TW593357B - Oxime ester photoinitiators having a combined structure - Google Patents

Abstract

Compounds of the formulae I, II, and III, wherein R1 is for example hydrogen, C3-C8cycloalkyl, C1-C12alkyl, phenyl unsubstituted or substituted; R2 and R2' for example are hydrogen, C1-C20alkyl, C3-C8cycloalkyl or phenyl, unsubstituted or substituted, or are formulae (A), (B), (C); Ar1 is for example phenyl, optionally substituted by e.g. formulae (D), (E) and/or (F); Ar2 is for example phenylene, optionally substituted e.g. by -(CO)R7, (D), (E) or (F); Ar3 is for example phenyl; M1, M2 and M3 are, for example, C1-C20alkylene; M4 is for example direct bond, -O-, -S-, -Y-(C1-C10alkylene)-Y'-, optionally substituted; Y and Y' are for example a direct bond or -O-; R7 is for example hydrogen, C1-C20alkyl or phenyl, optionally substituted; R8, R9, R8' and R9' are example hydrogen or C1-C12alkyl, exhibit an unexpectedly good performance in photopolymerization reactions.

Description

593357 A7 £ 7 ____ 5. Description of the invention (1) The present invention relates to a novel oxime ester having a combined structure containing an alkylaryl ketone, a diaryl ketone or an oxocoumarin, and its photopolymerizable composition Photoinitiator. From U.S. Patent No. 3558309, certain oxime ester derivatives are known as photoinitiators. In U.S. Patent No. 4,255,513, oxime ester compounds are disclosed. EP 810595 describes certain oxime esters having an electron-donating group. U.S. Patent No. 4,202,697 discloses arylamino substituted oxime esters. In JP 7-140658 A, Bull · Chem · Soc · Jpn · 1969, 42 (U)), 2981-3, BUU · Chem · Soc. Jpn. 1975, 48 (8), 2393-4 > Han9guk Somyu Konghakhoechi 1990, 27 (9), 672-85, macromolecule

{Macromolecules), \ 99 \, dl-Ί Anti-European Polymer Journal / J (European Polymer Journal), 1970, 933-943 ^, some ® ester compounds are described. In U.S. Patent No. 4,590,145 and JP 61-24558-A, several benzamoxifen compounds are disclosed. In Chemical Abstract, No. 96: 52526c ^ J. Chem. Eng. Data 9 (3), 403-4 (1964), J. Chin. Chem. Soc. (Taipei) 41 (5) 573- 8, (1994), JP 62-273259 · A (= Chemical Abstract 1: 83463w), JP 62-286961-A (= Derwent No. 88-025703 / 04), JP 62-201859-A (= Derwent No. 87-288481 / 41), JP 62-184056-A (= Derwent No 87-266739 / 38), US 5019482 and J. of Photochemistry and Photobiology A 107, 261-269 ( 1997), certain p-alkoxy-phenyloxime ester compounds are described. In the photopolymerization technology, there is still a need for photoinitiators that are highly reactive, easy to prepare, and easy to handle. In addition, this novel photoinitiator requires 4 (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 593357 A7

It meets the high requirements of the relevant properties of the industry, such as thermal stability and storage stability. Surprisingly discover compounds of formulae I, II and III

Wherein Ri is hydrogen, cvc: 8 ring alkyl or crc12 alkyl, which is unsubstituted or substituted with one or more halogen, phenyl and / or CN; or h is C2-C5 alkenyl; Phenyl, which is unsubstituted or substituted with one or more Ci_C6 alkyl, halogen, CN, OR3, SR4, and / or NR5R6; or R1 is q-C8 alkoxy, benzyloxy; or phenoxy Group, which is unsubstituted or substituted with one or more Ci-Q alkyl and / or halogen; R2 and R2 'are each independently hydrogen; unsubstituted alkyl or with one or more halogen, OR3 , Phenyl and / or Ci-C2 substituted with phenyl substituted with or3, sr4 and / or NR5R6. Alkyl; or r2 and r2, is (^^ cycloalkyl; or C ^ -C2. Alkyl, which is based on one or more ·-interrupted and / or optionally with one or more halogen OR3, phenyl, and / or phenyl substituted with 0r3, sr4, and / or nr5r6; or R2 and R2 'are phenyl, which are unsubstituted or substituted with one or more C, c6 alkyl, Substituted with phenyl, functional element, OR3, sr4, and / or NR5R6; or R2 and R2 'are alkyl or benzyl, which are unsubstituted or substituted with one or more Ci-C: 6 alkyl, Phenyl, 0r3, sr4 and / or NR5R6 substitution; R2 and R2 'are q-Cu alkoxycarbonyl groups, the selectivity of this paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read first Note on the back, please fill in this page again.) Order · · Line-593357 A7 _____ B7 V. Description of the invention (3) Replace with one or more -0- intermittent and / or optionally replace with one or more hydroxyl groups ; Or r2 and r2 'are phenoxycarbonyl groups, which are unsubstituted or substituted with crc6 alkyl, halogen, phenyl, or3, sr4, and / or nr5r6; or R2 and r2, which are CN, -conr5r6, no2 CrC4 _ alkyl, s (0) m-cv C6 alkyl; s (0) m • Phenyl, which is optionally substituted with Cl-C12 alkyl or so2-cvq alkyl; or so2o-phenyl, which is optionally substituted with 0vc12 alkyl; or diphenylphosphinofluorenyl or ((^ < 4alkoxy) -phosphinofluorenyl; or R2 and R2 'are as follows (please read the precautions on the back before filling this page)

ΑΓι is phenyl, naphthyl, benzamyl, or naphthyl, each of which is substituted with a prime, Ci-C ^ alkyl, C3-C8 cycloalkyl, benzyl, and / or phenoxycarbonyl 1 to 7 times; or each of them is substituted with phenyl or phenyl substituted with one or more 0r3, SR4 and / or NR5R6; or each of them is c2_Ci2 (Which is optionally substituted by one or more interruptions and / or optionally substituted by one or more hydroxyl groups); or each of them is substituted by OR3, SR4, SOR4, S02R4, and / or NR5R6, Wherein the substituent OR3, SR4, or NR # 6 optionally forms a 5- or 6-membered ring via, R4, Rs, and / or Han 6 and a further substituent on the phenyl or naphthyl ring; or each of them This paper replaces 6 paper standards with the following national standards (⑽> A4 size (21〇 < 297 public love) 593357 A7 B7 V. Description of the invention (4) • (CO) R7, suspected " % Ι〇-ΑΓ3 (D),

(¾ and / or

',' ·, / M except that if R2 is not an (eight), (B) or (C) group, ij ΑΓι is phenyl, naphthyl, benzyl, or naphthyl, each of which is at least Mono- (CO) R7, (D), (E) or (F) group substitution;

Ar2 is phenylene, naphthyl, phenylene dicarbonyl or arylene dicarbonyl, each of which is halogen, CrC12 alkyl, C3-C8 cycloalkyl, phenylfluorenyl, OR3, SR4, SOR4, S02R4 and / Or NR5R6 is substituted 1 to 4 times; or each is substituted with-(CO) R7, (D), (E) or (F) group; but if R2 or R2 'is not (A), (B) or (C) group and Ar2 is a phenylene, a naphthyl, a phenylene dicarbonyl, or a naphthyldicarbonyl group, then Ar2 is a group of (CO) R7, (D), (E) or (F) At least one substitution; if R2 is not hydrogen or (A), (B) or (C) radical, each is at least one of-(CO) R7, (D), (E) or (F) radical Replace, (Please read the notes on the back before filling this page)

Ar2 is additionally 0 0 or " 0,, 0 ", each of which is unsubstituted or substituted 1 to 4 times with halogen, crc12 alkyl, benzyl, or3, SR4 and / or NR5R6; or each It is replaced by-(CO) R7, 7 paper standards applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) 593357 A7 B7 V. Description of invention (5) (D), (E) or (F) group; If R2 is (A), (B) or (C) group, 〇 0

Ar2 is otherwise

CXX, each of which is unsubstituted or substituted 1 to 4 times with functin, Crcl2 alkyl, benzyl, OR3, SR4, and / or NR5R6; or each with _ (CO) R7, (D ), (E) or (F) group substitution; or Ar2 series (please read the precautions on the back before filling this page)

or

Each is unsubstituted or substituted 1 to 6 times with halogen, CrCu alkyl, benzyl, or3, SR4, and / or NR5R6; wherein the substituents OR3, Sr4, or NRsR6 are selectively via R3, R4, And / or R0 forms a 5- or 6-membered ring with one of the carbon atoms of the phenyl or naphthyl ring, or each of them is w_ (cq) r7. The size of this paper applies to the Chinese National Standard (CNS) A4 specification (210X297 (Mm) 593357 A7 ___B7 5. Description of the invention (6) (D), (E) or (F) group substitution;

Ar3 is phenyl, naphthyl or coumarin, each of which is substituted 1 to 7 times with halogen, crC12 alkyl, C3-C8 cycloalkyl, phenylfluorenyl, and / or phenoxycarbonyl; or each It is substituted with phenyl or with a phenyl substituted with one or more 0r3, SR4 & / or NR5R6; or each is c2_Ci2 alkoxycarbonyl (which is optionally substituted with one or more -0- is discontinuous and / or optionally substituted with one or more hydroxy groups); or each is substituted with OR3, SR4, SOR4, SO2R4, and / or NR5R6; M! Is C ^ -C2. Dextrinyl, optionally with one or more _〇_ discontinuities and / or optionally with one or more halogen, OR3, phenyl, or phenyl substituted with OR3, SR4, and / or NRSR0 Substitution; or phenylene or naphthyl, each of which is unsubstituted or substituted with one or more alkyl, phenyl, halogen, OR3, SR4 & or NR5R6; or% is a base as follows (Please read the notes on the back before filling this page)

It is optionally substituted 1 to 4 times with halogen, CVC12 alkyl, benzyl, or3, Sr4, soR4, So2R4, and / or NRsR6; wherein the substituents OR3, Sr4, or NRSR0 are selectively passed through, R4, and / or h form a 5- or 6-membered ring with one of the other carbon atoms of the phenyl ring; however, if Ar is phenyl, naphthyl, benzyl or naphthyl, each is Substituted by-(C0) -R7, fluorene, (E) or (F) group, then Mm is fluorene or fluorene, which is optionally substituted with halogen, CVC12 alkyl, phenylfluorenyl, OR3, SR4, s 〇R4, 9 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 593357 A7 __B7 5. Description of the invention (7) S〇2R4 and / or NR5R6 substituted 1 to 4 times; among them the substituents. R3, SR4, or NR5R6 optionally forms a 5- or 6-membered ring with one of the carbon atoms of other phenyl rings via R3, r4, r5, and / or &; M: a direct bond, crC1 () alkylene Or cyclohexyl; or m2 is alkynyl or alkylene-X_, each of which is optionally with one or more -0- interrupts and / or optionally with one or more halogen, OR3 , Phenyl or phenyl substituted with 0R3, SR4 and / or NR5R6 Generation; or m2 is extrinyl or naphthyl or phenyl-X- 'each is unsubstituted or with one or more crc6 alkyl, phenyl, halide, or3, sr4 & / or nr5r6 substitution; or m2 is CrC1 () alkylene-C (0) -X-, CVCi. Alkylene-X--C (0)-, phenylene-c (0) -x-, or CrC1Q alkylene-phenylene-X-; and M3 'are each a direct bond, Ci-C ^ Alkylene or cyclohexyl; or m3 and M3, are CrC1G alkylene or CVC1 () alkylene-X-, each of which is optionally interrupted by one or more -0- and / or Optionally substituted with one or more i-prime, OR3, phenyl or phenyl substituted with OR3, SR4 and / or NR5R6; or M3 and m3 'are phenylene, naphthyl or phenylene-X- , Each of which is unsubstituted or substituted with one or more Q-C6 alkyl, phenyl, halogen, OR3, SR4, and / or NR5R6; or m3 and M3, which are CVC10 alkylene-C (0 ) -X-, (VC1 () alkylene-XC (O)-, phenylene-c (0) -χ-, C1 () alkylene-phenylene-X- or phenylene -c (o) -phenylene; but each of the right Ari naphthyl, naphthyl or 2-R30-phenyl 'is not (C0) R7, (D), (E) or ( F) group substitution, then M3 and M3 'are not CVC10 Dendenyl-X-, Dendenyl-X- or Cj-C ^ o Dendenyl-Dendenyl-X-; This paper size applies to Chinese national standards ( CNS) A4 size (210X297mm) 10 (Please read the notes on the back before filling in this )

593357 A7 _B7_ V. Description of the invention (8) M4 and M4 'are each a direct bond, -〇-, -S-, -NR5'-, or -C0-; or M4 and M4' are -Υ- (〇ν〇 : 10 alkylene) -γ'_, which is optionally interrupted by one or more -0- and / or optionally by one or more halogen, or3, phenyl or OR3, SR4 and / Or NR5R6 substituted phenyl; or νι4 and M4 'are -Y-phenylene-Y'- or -Y-phenylene-Y' ·, each of which is unsubstituted or substituted by one or more Many of C "C6 alkyl, phenyl, halogen, 0r3, SR4 and / or nr5r6 substitution; or m4 and m4 'series -Y- (C" C4 alkylene) -0-phenylene alkyl)- Y'-or -Y-CC ^ -C ^ endenyl) -〇-naphthyl-endenyl) -Y'-; or M4 and M4'-endinyl-XC (o)-, the choice With one or more -0-discontinuities; or M4 and M / series, which optionally replace 1 to 1 with halogen, crc12 alkyl, benzyl, OR3, SR4, sor4, S02R4 and / or NR5R6 4 times; wherein the substituents OR3, SR4, or NR5R6 are optionally formed via R3, R4, R5, and / or cardiyl group with one of the other phenyl ring carbon atoms or a phenyl or naphthyl group attached to this group - Or 6-membered ring; M4 "is a direct bond, -0-, -S-, -NR5'_ or -C0-; or M4" is -YJCVCio (alkylene) -Y'-, which is optionally Or more -0- intermittent and / or optionally substituted with one or more halogen, OR3, phenyl or phenyl substituted with OR3, SR4 & or NR5R6; or phenylene -Y,- Or -Y-naphthyl-Y'-, each of which is unsubstituted or substituted with one or more CrC6 alkyl, phenyl, halogen, OR3, SR4 & / or NR5R6; or M4, -x-crc1 () Alkyl-XC (O)-, which is optionally interrupted by one or more _〇_; This paper size applies Chinese National Standard (CNS) A4 (210X297 public love) (Please (Read the notes on the back before filling out this page)

593357 A7 ______B7___ V. Description of the invention (9) X and X 'are each -0-, -S- or -NR5-; Y and Y' are each a direct bond, -ο-, -s- or -NR5- ; R3 is hydrogen, CVC2 () alkyl or phenyl-CVC3 alkyl; or R3 is (^-(: 8 alkyl, which is _〇H, -SH, -CN, C3-C6 alkoxy, _0CH2CH2CN, -OCI ^ CHdCCOCKCVQ alkyl), -O (CO)-(CVC4 alkyl), -0 (C0) -phenyl,-(CO) OH, and / or-(CCOCKCVQ alkyl) substitution; or R3 series c2-c12 alkyl, which is interrupted by one or more -0-; or R3--(CH2CH20) n + 1H,-((: Η2 (: Η20) η ((: 〇Η (νί: 8 alkane Base), C8 C8 base, C2-C12 base, C3-C6 base, C3-Cg ring base; or benzamidine, which is unsubstituted or one or more crc6 Alkyl, halogen, -0H and / or Ci-C ^ alkoxy substituted; or R3 is phenyl or naphthyl, each of which is unsubstituted or substituted with halogen, -OH, CrC12 alkyl, C "C12 alkyl Oxy, phenoxy, crc12 alkylsulfanyl, phenylsulfanyl, alkyl) 2 and / or diphenylamino; η is 1-20; R4 is hydrogen, alkyl, C2-C12 Diluted, C3-C8 cycloalkyl, phenyl-C, C3 alkane Or R4 is CVC8 alkyl, which is -OH, -SH, -CN, c3-c6 alkenyloxy, -OCH2CH2CN, -OCi ^ CHXCCOCKCVC ^ alkyl), _o (co) _ (cvc4 alkyl) , -O (CO) -phenyl,-(CO) OH, or-(C0) 0 (CVC4 alkyl); or r4 is c2-c12 alkyl, which is substituted by one or more -0- or- S-discontinued; or R4 (CH2CH20) n + 1H,-(CH2CH20) n (COHCrC8 alkyl), CVC8 alkylfluorenyl, c2-c12 alkenyl, c3-c6 alkenyl; or r4 phenylfluorene Fluorenyl, which is unsubstituted or substituted with one or more CVC6 alkyl, halogen, -OH, CVC4 alkoxy, or Cr 12 (Please read the precautions on the back before filling this page) This paper size applies to China Standard (CNS) A4 specification (210X297 mm) 593357 A7 B7 V. Description of the invention (10 C4 alkylsulfanyl substituted; or R4 is phenyl or naphthyl, each of which is unsubstituted or halogen, (Vc12 Alkyl, cvc12 alkoxy, phenyl-cvc3 alkoxy, phenoxy, q-Cu alkylsulfanyl, phenylsulfanyl, alkyl) 2, diphenylamino,-(C0) 0 (CrC8 alkyl),-(CO) -CVC8 alkyl or (CO) N (C "C8 alkyl) 2 substituted; R5 and R6 are each hydrogen, q-CM alkyl , C2-c4 hydroxyalkyl, c2-c10 alkoxyalkyl, C2-C5 alkenyl, C3-C8 cycloalkyl, phenyl-Ci-Cs alkyl, crc8 alkyl, c3-c12 · ene R5 and R6 are phenyl or naphthyl, each of which is unsubstituted or substituted with crc12 alkyl, benzyl, or (^-(: 12 alkoxy); or And r6—from c2-c6 # alkyl, which is optionally interrupted with -0- or -NR3 · and / or selectively with hydroxyl, alkoxy, (: 2-0: 4 alkylfluorenyloxy or Benzamidine oxygen substitution; R5 'is hydrogen, CVC2. Alkyl, c2-c4 hydroxyalkyl, C2-C1G alkoxyalkyl, c2-c5 alkenyl, c3-C8 cycloalkyl, phenyl-CVC3 alkyl, CVC8 alkyl, C3-C12-ene Group, benzamyl group; or r5, phenyl or naphthyl, each of which is unsubstituted or a q-Cu alkyl group or (^-(: 12 alkoxy group)

Generation; or R5 'is a% group; R7 is hydrogen, CrC2Q alkyl group; cr C8 alkyl group, which is based on i prime, phenyl, -OH, -SH, -CN, C3-C6 alkenyloxy, -OCH2CH2CN , -0CH2CH2 (C0) 0 (CVC4 courtyard), -0 (C0) _ (C1-C4 alkyl), _〇 (c〇) _ phenyl,-(CO) OH or-(co) o (cvc4 Alkyl) substitution; or c2_cl2 alkyl, which is one or more -0 · discontinued; or R7- (CH2CH20) n + 1H,-13 (Please read the precautions on the back before filling this page ) This paper is oriented towards the Zhongguanjia standard (_ A4 size ⑽ x297). 5.93357 A7 ____B7 5. Description of the invention (11) (Please read the precautions on the back before filling this page) (CK ^ CI ^ OWCOHCVQ alkyl), C2-C12 alkenyl or C3-C8 cycloalkyl; or R7-based phenyl, biphenyl, or naphthyl, each of which is optionally one or more (^ -ί: 6 alkyl, halogen, CN, or3, sr4, sor4, so2r4, or NR5R6 substitution, wherein the substituents OR3, SR4, or NR5R6 are selectively substituted via R3, R4, R5, and / or cardio with the carbon atom of the phenyl, biphenyl, or naphthyl ring One forms a 5- or 6-membered ring; R8, R9, R8 ′ and R9 ′ are each independently hydrogen, CVCu alkyl, and their selection Substituted with one or more halogen, phenyl, CN, -OH, -SH, c "c4 alkoxy,-(CO) OH or-((: 0) 0 ((ν (: 4 alkyl) ; Or R8, R9, r8, and R9 'are phenyl groups, which are optionally substituted with one or more CrC6 alkyl, halogen, CN, OR3, sr4, or NR5R6; or R8, R9, r8, and r9, are Halogen, CN, or3, sr4, sor4, so2r4 or nr5r6; wherein the substituents or3, sr4 or nr5r6 are optionally via the r3, r4, r5 and / or r6 group with the phenyl, naphthyl, benzyl or One of the carbon atoms of the naphthyl group or the substituent R7 or one of the carbon atoms of the naphthyl or phenyl group of M3 forms a 5- or 6-membered ring; or R8 and R9 or R8 'and R9' together are I10 ? 11 I12 ί13, ΡΗ η — ^ c = c—c = c—or —c = c—c—ο—group;

Rio, Rii, Ri2, and Ri3 are each independently hydrogen, Ci-Cu alkyl, which are optionally selected from one or more halogen, phenyl, CN, -OH, -SH, CrC4 alkoxy,-(CO ) OH or-(C0) 0 (CrC4 alkyl); or ho'Rn, R12 and R13 are phenyl groups, optionally with one or more C1_C6 alkyl, halogen, CN, OR3, SR4 or NR5R6 Replace; or Rio, Ru, Ru This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 14 593357 A7 B7 V. Description of the invention (12 (Please read the precautions on the back before filling this page) and R13 Halogen, CN, OR3, SR4, or NR5R6; and Rm and R15 are each independently hydrogen, CrC12 alkyl, which is optionally substituted with one or more halogen, phenyl, sulfide-011, -811, (: 1-(: 4 alkoxy,-((: 0) 011 or-(co) o (crc4 alkyl)); or R14 and R15 are phenyl, optionally with one or more crc6 alkyl, Dentin, cn, or3, sr4, or nr5r6 are substituted; however, if Aq is phenyl, it is substituted with (E) and not additionally substituted with (D) or (F) and R2 is hydrogen, then M4 is not directly (Ii) if Al is naphthyl, it is E) is substituted without additional (D) or (F) groups, then M4 is not directly constructed, S, 0 or NR5;-, ^ τ · (in) if M * is 0 and & is hydrogen, then Aq is a phenyl group that is not substituted with (E) group and is not additionally substituted with (D) or (F) group and at the same time is substituted with 0r3 or sr4, nr5r6, phenyl,-(co) r7 or so2r7 (Iv) if Aq is phenyl, which is substituted with-(CO) R7 and is not additionally substituted with (D) or (F), then R2 is non-hydrogen; (v) if Aq is phenyl, it is _ (c〇) R7 is substituted without additional (D) or (F) groups and & non-hydrogen, then R7 is not phenyl or Ci_Cu alkyl; (vi) if Aq is naphthyl, it is _ ( c) R7 is substituted without additional (D) or (F) groups, then R7 is not a phenyl group or a GVCn alkyl group; compared to the individual structure of the photoinitiator or its predominant mixture, it exhibits in photopolymerization reactions Unexpectedly good performance. Substituted aryl groups ΑΓι, Ar2, Ar3, M4 or M4 are individually substituted 1 to 7, 1 to 6 or 1 to 4 times. Obviously, the defined aryl groups are not

15 593357 A7 _______B7_ 5. Description of the Invention (l3) It can have more substituents than the free position of the aryl ring. These groups are substituted 1 to 7 times, for example, 1 to 6 times or 1 to 4 times, especially one, two or three times. The substituted phenyl group is substituted 1 to 4 times, for example, one, two or three times, and especially two times. The substituent on the phenyl ring is preferably at position 4, or a 3,4-, 3,4,5-, 2,4 ·, or 2,4,6- structure on the phenyl ring. Naphthyl is 1-naphthyl or 2-naphthyl. Qinyi is 1-naphthyl or 2-naphthyl. Coumarin-based

Preferably, it is a 1-coumarin group, a 4-coumarin group or a 5 · coumarin group. The phenylene group is 1,2-phenylene, 1,3-phenylene or ι, 4-phenylene, and more preferably 1,4-phenylene. Dextrin-based 'for example, 1,2-, 1,3-, 1,4-, 1,5-, 1,6_, 1,8-, 2,3-, 2,6-, or 2,7- Naphthyl. The phenylene dioxy group refers to a phenylene group substituted with a 20 atom. Examples are phenylenedioxy, 1,3-phenylenedioxy or 1,4-phenylenedioxy, and more preferred is 1,4-phenylenedioxy. A naphthyldioxy group means a naphthyl group substituted with a 20 atom. Examples are i, 2_, i ,; ^, 14_, 15_, 16, U, 2, 3, 2, 6 or 2,7-naphthyldioxy. ’(Please read the notes on the back before filling out this page)

593357 A7 _______B7_ V. Description of the invention (14) (Please read the notes on the back before filling out this page) The CVCm department is linear or branched and department, for example, CVCu-'CrCu-'Ci-CV'CVCV or ( VCV amyl or c4-C12- or C4-C8-alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, pentyl Base, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, ten Hexyl, octadecyl, and eicosyl. Crc12 alkyl, c2-c12 alkyl, c_cnalkyl, crc8 alkyl, and CrC6 alkyl have the same definitions for CVC2 as above. The alkyl radicals have the same definitions as the highest. Up to the corresponding number of carbon atoms. One or more -0-intermittent CVCm firing system, for example, -0_ interrupted 1-9, 1-5, 1-3 times or once or twice. 2 0 The atomic system is separated by at least dimethyl (ie, ethyl). Alkyl is linear or branched. For example, Dingulene structural units occur, -CH2-CH2-0-CH2CH3,-[CH2CH20] y- CH3, Where y = l-9,-(ch2-ch2o) 7-ch2ch3, -CH2-ch (ch3) -o-ch2-ch 2ch3 or · ch2-ch (ch3) -0-ch2-ch3 〇CVC ^ o sintered base is linear or branched and system, for example, (VCu-, cvCi.-, cvcv, cvcv or cvc4- sintered c4-c12- or C4_C8 alkynyl. Examples are dimethyl, ethyl, propyl, methyl, butyl, methyl, ethyl, 1,1_ Fluorenyl, ethyl, dimethyl, pentyl, pentyl, hexyl, heptyl, 2-ethyl hexanyl, octyl, danyl, decyl, and dodecyl Fourteen alkyl groups, Fiveteen alkyl groups, Sixteen alkyl groups, Eighteen alkyl groups, and Eighteen alkyl groups. The alkyl groups have the same meaning as shown above for Cl_c2G alkyl groups, and the highest correspondence is The number of carbon atoms. This paper is based on the Chinese national standard (⑽A4 size ⑵⑽Tear Fantasy-17-593357 A7 ___B7_ V. Description of the invention (15) Cyclohexyl system 1,2-, 1,3 · or 1,4- Cyclohexyl. C ^ -C4 via alkyl refers to a c2_c4 alkyl group substituted with one or two 0_ atoms. The alkyl group is straight or branched. Examples are 2-hydroxyethyl, ι_hydroxyethyl, 1 -Ethylpropyl, 2-Ethylpropyl, 3.Ethylpropyl , 1-Ethylbutyl, 4-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 2,3 · dihydroxypropyl or 2,4-dihydroxybutyl. C; 3-C8 ring The alkyl group is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, especially cyclopentyl and cyclohexyl.

CrCu alkoxy is a Ci_Ci2 alkyl substituted with one 0-atom. CrCu alkyl has C ^ C: 2 as above. Alkyl has the same meaning, up to the corresponding number of C atoms. CrC4 alkoxy is linear or branched, for example, fluorenyloxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy, third butoxy.

Ci-Cu alkylsulfanyl is substituted with one S- atom (^-(: 12 alkyl. Ci-C) 2 alkyl has the same meaning as shown above for Cj-C ^ alkyl, up to Corresponding number of C atoms. Crc4 alkylsulfanyl is linear or branched, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, n-butylsulfanyl Group, second butylsulfanyl group, isobutylsulfanyl group, third butylsulfanyl group. C2_C1 () alkoxyalkyl is a c2_ci () alkyl group interrupted by a 0-atom. C2_c1 () The alkynyl group has the same meaning as shown above for cvc ^ o, and the most corresponding number of C atoms is Nanda. Examples are methoxyfluorenyl, methoxyethyl, methoxypropyl, and ethoxyfluorene Base, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl. This paper size applies to China National Standard (CNS) A4 specifications (210X297 public love) '' ^ " (Please read the notes on the back before filling this page)

593357

G-C2. Alkyl groups are linear or branched and are, for example, C2_c ^ _, c2-c14- ^ c2.c12 ^ c2.c8 ^ c2.c6. ^ C4-c12. Or C4_C8_alkanoyl. Examples are ethenyl, propionyl, butylamyl, isobutylamyl, pentamyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, ten Pentadecyl, hexadecyl, octadecyl and eicosylfluorenyl are preferred, and ethyl fluorenyl is preferred. Alkyl groups have the same definition as shown for alkyl groups above, up to the corresponding number of carbon atoms.

CrC: 4 Alkyloxy is linear or branched. For example, ethynyloxy, propionyloxy, butyryloxy, isobutyryloxy, and more preferably ethynyloxy.

CrCi2 alkoxycarbonyl is linear or branched and is, for example, methoxy Ik, ethoxychi, propoxychi, n-butoxychi, isobutoxycarbonyl, 1,1-di Methylpropoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonoxycarbonyl, decoxycarbonyl or dodecyloxycarbonyl, especially methoxycarbonyl , Ethoxycarbonyl, propoxychi, n-butoxychi or isobutoxyweiyl, preferably methoxycarbonyl. It is straight or branched with one or more -0-intermittent (: 2- <: 12 alkoxycarbonyl groups. Di-0-atoms are separated by at least two methyl groups (ie, ethyl groups). Phenoxycarbonyl system. The substituted phenoxycarbonyl system is substituted 1 to 4 times, for example, 1, 2 or 3 times, especially 2 or 3 times. The substituent on the phenyl ring is preferably a phenyl group. 4 position on the ring, or 3,4-, 3,4,5-, 2,6-, 2,4-, or 2,4,6- position, especially 4 or 3,4-position 19 (please Please read the notes on the back before filling this page.) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 593357 A7 ------ B7___ 5. Description of the invention (17) ~-^. Benzene Alkyl systems are, for example, benzyl, phenylethyl, methylbenzyl or α, α-dimethylbenzyl, especially benzyl. Alkenyl may be mono- or polyunsaturated and System, such as vinyl, allyl, fluorenylallyl, 1 ,; μ dimethylallyl, butenyl, 3 · butenyl, 2-butenyl, 1,3-pentane Alkenyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. C2-C5 alkenyl has the above It has the same meaning for the c2-ci2 alkenyl group, and up to the corresponding carbon number. The q-C6 alkenyl group can be mono- or polyunsaturated and is, for example, allyloxy, methallyl Alkyloxy, butenyloxy, pentenyloxy, H pentenyloxy, 5-hexenyloxy. C3-C12 alkenyl may be mono- or polyunsaturated and is, for example, , Propynyl, 2-methyl-propenyl, butenyl, pentenyl, -pentadienyl, 5-hexenyl. C3-C6 alkenyl has the same properties as above for c3_Ci2 Alkenyl has the same meaning, up to the corresponding carbon number. Halogen is fluorine, gas, bromine or ethene, especially fluorine, gas and bromine, preferably fluorine and gas. If phenyl, naphthyl or benzamidine The substituents or3, sr4, and NRsR6 on the basic ring form a 5- or 6-membered ring through the R3, R4, Rs, and / or R0 group and further substituents on the phenyl or naphthyl ring, including bi- or tri-ring (including The structure of phenyl ring) was obtained. The example is that the paper size applies the Chinese national standard (CN5J) A4 specification (210x297 mm) 20 (Please read the precautions on the back before filling this page}

593357 A7 B7

5. Description of the invention

COO goods. Ος ^, Οςχ >

C2H5 if used as M4 or M4 ’

~ X

The substituent OR3, SR4 or nr5r6 on the group optionally forms a 5- or- A 6-membered ring, a structure containing a bi- or tri-ring (including a phenyl ring) is obtained. Example department

If, for example, ruler 8, ruler 9, ruler 8 and ruler 115, ruler 6 and 6, the substituent cis 5116 via R5 and / or R6 via phenyl, naphthyl, benzyl or naphthyl fluorene (Please Read the precautions on the back before filling in this page), one of the carbon atoms of the | group forms a 5- or 6-membered ring, the following structures are preferred specific examples 0 ^ χ > ·, such as Οζχ >, 〇φ3 · ,

Crc12 • Hyunji 0H3 c2h5 63η7 ° ^ 9. Clearly, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied in the context of the definition of the present invention and based on the template paper size. 593357 Description of the invention (as shown in the example of i9, these bases can carry further substituents. If used as I and / or &amp; The mono- or substituents selectively form a 5- or 6-membered ring, and a structure containing a bi- or tri-ring (including a phenyl ring) is obtained. Examples are 00, <X; X)

Che Xiajia is a compound of chemical formulas i, II and Ri, wherein Ri is C3_C: 6 cycloalkyl or C ^ C: 6 alkyl, which is unsubstituted or substituted with one or more halides or phenyl groups; or I is phenyl, which is unsubstituted or substituted with one or more C, C6 alkyl, halogen, 0r3, sr4, and / or NR5R6; or Ri is Ci-C ^ alkoxy or benzyloxy R2 and R2 'are each independently hydrogen; Cr C20 alkyl optionally substituted with one or more halogen, phenyl, and / or phenyl substituted with OR3, SR * and / or NR5R6; or Cs -C: 6 cycloalkyl; or C2-C2G alkyl, which is interrupted by one or more -0- and / or optionally by one or more halogens, 0r3, phenyl and / or OR3 , SR * and / or NR5R6 substituted phenyl; R2 and R / is phenyl, which is unsubstituted or substituted with one or more Ci-C6, phenyl, halogen, OR3, SR4 and / or NR5R6 Substitution; or r2 R2 'is C2-C12 hydrazone, C2-C12 alkoxycarbonyl or (a), (B) or (C) or alkane and (Please read the precautions on the back before filling this page), ? τ— This paper size applies to Chinese national standards (CNS> Α4 size (210 X 297 mm) twenty two

593357 A7 ____ B7____ V. Description of invention (20) basis;

Ar〗 is a base, naphthyl or benzyl group, each of which is substituted 1 to 7 times with halogen, Ci_C6 alkyl, OR3, SR4, and / or NR5R6; or each of them is substituted with phenyl or Substituted with one or more phenyl groups substituted with OR3, SR4 or NR5R6; or each of them is substituted with a (CO) R7, (D), (E) and / or (F) group;

Ar2 is phenylene or phenylphenylene, each of which is substituted 1 to 4 times with halogen, CrC6 alkyl, OR3, SR4 &amp; or NR5R6;

Each is unsubstituted or substituted 1 to 4 times with halogen, alkyl, OR3, SR4, and / or NR5R6; or each is-(c〇) R7, (D), (E) or (F ) Group substitution; or each of Aγ2's is unsubstituted or substituted 1 to 6 times with oxine, C, C6 alkyl, OR3, SR4 and / or NRSR6, wherein the substituents OR3, SR4 or NR5R6 are selected To form a 5- or Bu ring through one of the carbon atoms of the phenyl ring via the R4, R4, and R0 groups and / or R0 groups; or each paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public director) &quot; a &quot; &quot; -23 二 &quot; 一 &quot; '—' (Please read the notes on the back before filling this page)

593357 A7 _B7 _ 5. Description of the invention (21) One is substituted with-(CO) R7, (D), (E) or (F) group;

Ar3 is phenyl, naphthyl or coumarin, each of which is substituted 1 to 7 times with halogen, alkyl, phenyl or phenyl substituted with one or more OR3, SR4 &amp; or NR5R6; Or each is substituted with OR3, SR4, and / or NR5R6; is Ci-Ca alkylene, which is optionally interrupted by one or more -0-; or M1 is phenylene or naphthyl, each One is unsubstituted or substituted with one or more CVC6 alkyl, phenyl, halogen, OR3, SR4, and / or NR5R6; or%) groups, which are optionally substituted with halogen, C, C6 alkyl , OR3, SR4, and / or NR5R6 are substituted 1 to 4 times, wherein the substituent OR3, SR4, or NR5R6 optionally forms 5- through R3, R4, R5, and / or cardiyl with one of the other phenyl ring carbon atoms Or 6-membered ring; M2 is a direct bond, CVCw alkylene or CrC1 () alkylene-0-, each of which is optionally interrupted by one or more -0-; or M2 is benzene -0-, which is unsubstituted or substituted with one or more CrC6 alkyl, phenyl, halogen, OR3, SR4, and / or NR5R6; or m2 is cvc1 () alkylene-phenylene-0 -;

Mg and Μ / are each a direct bond to each other, or are CrCw sintered or sintered -X- 'each of which is selectively interrupted by one or more _〇_; or M3 and Μ / Phenyl or phenylene-X-, each of which is unsubstituted or substituted with one or more CVC0 alkyl, phenyl, halogen, OR3, Sr4, and / or NR5R6; or M3 and m3 'are crc1 ( ) Alkylene-C (0) -X-, c10 alkylene-XC (o) ·, phenylene-C (0) -X-, CVCi. Alkylene_Xylenyl-X- or Xylenyl-C (0) -Xylenyl; This paper size applies to China National Standard (CNS) A4 (210X297 mm) 24 (Please read the notes on the back first (Fill in this page again)

593357 A7 _ B7__ V. Description of the invention (22) M4 and M / are each a direct bond, -0-, _s-, -NR5'- or -CO-; or M4 and M4 'are -Y- (CrC1 () (Alkylene) -Y'-, which is optionally interrupted by one or more -0-; or μ4 and M4 'are -fluorene-phenylene-fluorene'-, each of which is unsubstituted or Substituted with one or more C ^ -C ^ alkyl, phenyl, halogen, OR3, SR4, and / or NR5R6; or M4 and M4'-Y- (CrC4 alkylene) -0-phenylene -〇- (CVC4alkylene) -Y'- or -Y- (CVC4alkylene) -〇-alkylene-CKCVQ alkylene) -Y'-; or M4 and M4'-X-CkC !. Alkylene-x-c (o)-, optionally between one or more zeros

Cj-broken; or M4 &amp; M4 'is a UU group, which is optionally substituted 1 to 4 times with dentin, CVC12 alkyl, OR3, SR4 and / or NR5R6; wherein the substituents OR3, SR4 or NR5R6 are selectively Form a 5- or 6-membered ring via R3, R4, R5 and / or a heart group with one of the carbon atoms of another phenyl ring or a phenyl group attached to this group; with a 4 "system direct bond, -0-, -3-,-\ 115'- or-(: 〇-; or% 4 '' is -Ya-((: 1-(: 10 alkylene) -Y'-, which is optionally one or more More than -0-discontinued; or m4 "is -Y-phenylene-Y'-, which is unsubstituted or substituted with one or more (^-(^ alkyl, phenyl, functional element, 〇R3 , SR4 and / or NR5R6; or m4 "is -X-CVC1 () alkylene-XC (O)-, which is optionally interrupted by one or more -0-; R3 is hydrogen, alkyl or Phenyl-C ^ -C ^ alkyl; or squaryl, which is substituted with c3-c6 alkenyloxy, -ckcomcvg alkyl), _〇 (co) _phenyl; or r3 is c2-c12 alkane Based on one or more -ο-interruptions; or r3 based on CVC8 alkyl fluorenyl; or phenyl fluorenyl based on unsubstituted paper This paper applies Chinese National Standard (CNS) A4 (210 X 297) Mm 25 (Please read the notes on the back before filling out this page). Order · ♦ 593357 A7 ______ B7 V. Description of the invention (23) or substituted with one or more Crc0 alkyl, halogen and / or Ci_c4 alkoxy; Or R3 is phenyl or naphthyl, each of which is unsubstituted or halogen, (please read the notes on the back before filling this page) alkyl, CrC4 alkoxy, Ci-Cu alkylsulfanyl, Phenylsulfanyl, NCCVCu alkylh and / or diphenylamino substitution;., Tr- &amp; hydrogen, CVC2. Alkyl or phenyl_Cl_c3 alkyl; or heart alkyl, which is Substituted with (33- &lt;: 6 alkenyloxy, -CKCOXCi-C ^ alkyl) or -O (CO) -phenyl; R4 is a CVC ^ 2 alkyl group, which is interrupted by one or more; or R4 is a C "C8 alkylfluorenyl group; or a benzamidine group, which is unsubstituted or substituted with one or more CrC6 alkyl, halogen, alkoxy, or C! -C4 alkylsulfanyl, or R4 Are phenyl or naphthyl, each of which is unsubstituted or halogen, C? _C12 alkyl, CrCu alkoxy, phenoxy, cr C12 alkyl, phenylthio, -N ( CrC12 alkyl) 2, diphenylamino or-(CC ^ CKCVCs alkyl) substituted; 5 and X are each independently hydrogen, crc2G alkyl, c2-c1G alkoxyalkyl, phenyl-crc3 alkyl, CrC8 alkyl or benzamyl; or X and R6 are phenyl or naphthyl, which Each is unsubstituted or substituted with benzamyl, cvc12 alkyl or crc12 alkoxy; or chi 5 and r6—from c2-c6 alkylene, optionally with -0 or -NR3 -Intermittent and / or optionally substituted with CVC4 alkoxy, c2-c4 alkylfluorenyloxy or benzamyloxy; R5 'is hydrogen, CVCi. Alkyl or C2-C4 hydroxyalkyl; or R5 'is phenyl or naphthyl, each of which is unsubstituted or C, C6 alkyl or Ci-Q alkoxy

Radical substitution; or r5 'is R® radical; this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 26 593357 A7 __ B7 V. Description of the invention (24) R7 hydrogen, CVC2 alkyl; Crc8 Alkyl, which is substituted with phenyl, -0H, -0 (C〇)-(crC4alkyl) or -O (CO) -benzyl; or C2-C5 alkenyl or C3-C8 cycloalkyl ; Or r7 is phenyl, biphenyl, or naphthyl, each of which is optionally substituted with one or more CVC6 alkyl, halogen, CN, OR3, SR4, or NR5R6; R8, R9, R8, and R9 , Each independently hydrogen, CVC6 alkyl; phenyl, which is optionally substituted with one or more CVC6 alkyl, halogen, or3, sr4 * nr5r6; or r8, r9, r8, and r9, which are halogen, or3, sr4 or nr5r6; wherein the substituents or3, sr4 or NR5R6 are optionally formed via the R3, r4, R5 and / or R6 group with the carbon atom of the phenyl, naphthyl or benzamidine group of Aq—or the substituent R7 5-or 6 · membered ring, or R8 and R9 or 'and R9, ^ 10 ^ 11 ^ 12 ^ 13 together are a group; and

RlO, Rll, Rl2, and Rl3 are each independently hydrogen, alkyl, phenyl, halogen, OR3, SR4, or NR5R6. Particularly preferred are compounds of formula I or III, wherein Ri is C, C6, C6, Oxy or phenyl 'is unsubstituted or substituted with one or more C "C4 alkyl, halogen or OR3; 112 and R2' are each independently hydrogen or CrCw alkyl;

An is phenyl, naphthyl or benzamidine, each of which is substituted with halogen, halo, OR3, SR4, NR5R6, phenyl or phenyl substituted with one or more of SR4 or NRSR6 To 7 times; or each of them is replaced by the following: This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). Watching 丨 i ---- line 丨 593357 A7 B7 V. Description of the invention (25 • Μ 厂 〇ΗΓϋ—

but

Aq is phenyl, naphthyl or benzamidine, each of which is substituted with at least one of c (〇) r7, (D), (E) or (F) group; Phenyl, which is not substituted with (D) or (F), but substituted with (E), and r2 is hydrogen, then μ4 is not directly formed, S or NR5; (ii) if ΑΓι is naphthyl, it is Not substituted with (D) or (F) but substituted with (E), then M4 is not directly constructed, S, 0 or NR5; (iii) If M4 is 0 and R2 is hydrogen, then Ar! Is not ( E) a phenyl group substituted with ortho or SR4, NR5R6, phenyl, -COR7, or S02R7 in the ortho position; (iv) if ΑΓι is phenyl, it is not (F) group substituted but substituted with COR7 group, then R2 is non-hydrogen; (v) if Aq is phenyl group, which is not substituted with (D) group or (F) group but substituted with COR7 group and R2 is not hydrogen, then R7 is not phenyl or Ci-Cu alkyl; (vi) if AΓι is naphthyl, which is not substituted with (D) or (F) but substituted with COR7, then R7 is not phenyl or Ci_Cn alkyl; This paper size applies the Chinese national standard (〇 ^) A4 specification (21〇 &gt; &lt; 297mm) 28 (Please read the notes on the back first Complete this page)

593357 A7 B7 V. Description of the invention (26

Ar2 series 0 〇

M4 "

, Each of which is unsubstituted or substituted 1 to 4 times with halogen, CrC6 alkyl, OR3, sr4, or NR5R6; Ar3 is phenyl or naphthyl, each of which is halogen, C, C6 alkyl, 〇R3, sr4, NR5R6, phenyl or phenyl substituted with one or more 〇R3, SR4 or NR5R6 substituted 1 to 7 times; M4 and M4 'are each a direct bond, -0-, -S-, -NR5,-or -C0-; or M4 and M4 'Department -YJCi-CiQ Extend the base) -Y'-' It is optional to one (Please read the precautions on the back before filling this page) • Order —

Or more -0-discontinued; or M4 and M4 'groups which are optionally substituted 1 to 4 times with halogen, (VC6 alkyl, OR3, SR4 * NR5R6; X and X' are each -0-, -S- or -NR5-; meaning 3 is q-CM alkyl, phenylfluorenyl, phenyl or naphthyl; R4 is C ^ C ^ o alkyl, benzyl, phenyl or naphthyl; R5 and R6 Each of them is hydrogen, CrC20 alkyl, benzyl, Cl-c8 alkyl, methylbenzyl, methyl or qynyl, or 1 and R6 together are C2-C6 alkylene, which are optionally- 〇-or-NR3-discontinued; R7 is hydrogen or C ^ -C ^ q alkyl; R7 is phenyl or naphthyl, each of which is 29 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 593357 A7 B7 V. Description of the invention (27 Nature substituted with one or more CVC6 alkyl, halogen, 0r3, sr4 or NR5R6;

Rs and R9 are each hydrogen, alkynyl, or phenyl optionally substituted with one or more C, C6 alkyl, halogen, OR3, SR4, or NR5R6; R8 and r9 are prime, or3, sr4, or nr5r6 ; Wherein the substituents OR3, sr4, or NRsR6 optionally form 5- ^ via one of the carbon atoms of the phenyl, naphthyl, or benzamyl group with the R3, R4, r5, and / or r6 group or the substituent r7 10 ^ 11 ^ 12 ^ 13 -C = C—C = C- f (Please read the precautions on the back before filling out this page) or 6-membered ring; or R8 and R9 — starting line — one base, where R10 , Rn, R12 and R13 are each independently hydrogen, CrC6 alkyl, phenyl, halogen, OR3, SR4 or NR5R6 〇,?! 1 Compounds of further interest are compounds of formula I or III, where R! Is CVC12 alkyl Radical or phenyl radical; 2 and r2 'are hydrogen or cvc12 alkyl;

Aq is a phenyl, naphthyl or benzamidine group, each of which is substituted with 0r3 or NR5R6; wherein the substituent NR5R6 is optionally formed via a r5 or a 6-base group with a further substituent on the phenyl or naphthyl ring 5- or 6-membered ring; or each of them is substituted with-(CO) R7, (D), (E) or (F) group; WWWV; Aγ3 is naphthyl; m4 and M4 'are each directly Bond, -s- or -Y- (CrC1 () alkylene) _ Y'-; Y and Y 'are each a direct bond or; 30 This paper size applies Chinese National Standard (CNS) A4 specification (21〇x297 Public love) 593357 A7 B7 V. Description of the invention (28 R3 series alkyl group; R4 series phenyl group, which is unsubstituted or substituted with Xing alkyl group); R5 and R6 are each Ci_Ci2 alkyl group or phenyl group; R7 series Phenyl, biphenyl, or naphthyl, each of which is optionally substituted with one or more CVC6 alkyl, halogen, OR3,%, or pyrene; and R8 and R9 are hydrogen. Of particular interest are compounds of formulae I and III, the center of which is alkyl or phenyl; R2 and R2 'are hydrogen, CVC12 alkyl, phenyl or c2_Ci2 alkoxycarbonyl; Aq is phenyl, naphthyl or benzene Formamyl groups, each of which is substituted with 0r3 or Nr5r6; wherein the substituent NR5R6 optionally forms a 5- or 6-membered ring via a r5 or a 6-base and a further substituent on a phenyl or naphthyl ring; or Each of them is substituted with-(CO) R7, (D), (E) or (F) group;

Ar2 is yv ν ν; Aγ3 is naphthyl; M4 and M4 'are each a direct bond, and Se ^ -Y- (crc1 () arsenyl) -Y'- or -Y- (CrC4alkylene)-. -Phenylene_〇_ (crC4alkylene) -Y, _; Υ and Υ 'are each a direct bond or; R3 is cvc12 alkyl; R4 is phenyl, which is unsubstituted or with-(COXCi -Cs alkyl) substitution; Heart and R6 are each an alkyl group; or phenyl group which is unsubstituted or substituted with benzamyl or C1-C12 alkyl; This paper size applies Chinese National Standard (OiS) A4 specifications ( 21〇χ297mm) 31 (Please read the notes on the back before filling out this page) Order — 593357 A7 B7 V. Description of the invention (29) R7 is base, biphenyl or naphthyl, each of which is selective Is substituted with one or more CrC6 alkyl, halogen, 0r3, sr4 or NR5R6; and Rs and &amp; are hydrogen or NR ^ R6, wherein the substituent NR5R6 is optionally via the R5 or R6 group and the phenyl group of A One of the carbon atoms of the naphthyl or benzamidine group forms a 5- or 6-membered ring. Particularly preferred compounds according to the present invention are 1- [4- (4-benzylidene-phenylsulfanyl) -phenyl] -oct-1-oneoxime-〇_acetate, 1β (6-benzene Formamidine-9-ethyl · 9 · Η · -carbazol-3-yl) -oct-1-oneoxime acetate, ^ (4- (444- (4-butamyl_phenylsulfanyl)) _Benzylsulfanyl] _phenylsulfanylphenyl, &gt; butanyl q-ketooxime-0-acetate, 1- [4 · (4- {4- [4- (1-ethoxyl Amine-butyl) -phenylsulfanyl] -benzylidene} -phenylsulfanyl> Phenylketoxime acetate S. Preferred compounds of formulae I, II and III are characterized by at least one The ester portion and at least one alkylaryl ketone, diaryl ketone, fluorenyl coumarin or aryl coumarin portion are not combined in one molecule with a short spacer. Chemical formulas I, II and The oxime esters of III are prepared by methods described in the literature, for example, by inert solvents (e.g., tertiary butyl methyl ether, tetrahydrofuran (THF), or dimethylformamide) and by bases (e.g., triethyl) Amine or sting) to react the corresponding oxime with a fluorenyl gas or anhydride in a basic solvent such as σ-pyridine. ----------------- ----fee ： (Please read the precautions on the back before filling this page)-, \ t— CHR1 or R ~ 〇-R1 base? Η Ⅱ II Art—C—R2? -Ri N II Art—C—R2 (I) 32 This paper is suitable for financial standards (⑽A4 size⑽χ297 public love) 5193357 A7 ___ B7_ V. Description of the invention (30) This reaction is known to those skilled in the art, and is generally between -15 and +50 ° C ( It is preferably performed at a temperature of 0 to 25 ° C. The compounds of Chemical Formulae II and III are similarly obtained by using an appropriate oxime as a starting material: Η—ΟI ΝII Ar1-C Aq, Ar2, R2 and R2 ′ have The meaning is shown above. The oxime required as a starting material can be obtained by standard chemistry textbooks (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) or specific monographs ( For example, SR Sandler &amp; W. Karo, Organic functional group preparations, Volume 3, Academic Press). One of the most convenient methods is, for example, in ethanol or ethanol Aldehyde or ketone and hydroxyl Amine. In this case, a base such as sodium acetate or pyridine is added to control the reaction mixture was pH® known reaction rate of the system by pH dependent, and based on experience at the start or continuously during the reaction. Basic solvents (such as pyridine) can also be used as bases and / or solvents or co-solvents. The reaction temperature is generally the reflux temperature of the mixture, and is generally about 60-120 ° C. Another convenient way to synthesize oxime is the "active" nitrosation of methylene with nitrite or alkyl nitrite. Test conditions (eg, as described in Organic Syntheses coll. Book VI (J. Wiley &amp; Sons, New York, 1988), pages 199 and 840) and acid strips -M12 or Η— (j) (j)一 Ηίί II • C-Ar Factory C-R2 '(Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 33 593357 A7 __B7_ V. Description of the invention (31) (eg, as described in Organic Synthesis coll. Book V, pages 32 and 373, coll. III book, pages 191 and 513, coll. Book II, pages 202, 204 and 363) Suitable for making bricks as starting materials for the present invention. Nitrite is generally produced from sodium nitrite. The alkyl nitrite may be methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite. Each oxime ester group may exist in a two structure ((Z) or (E)). It is possible to separate these isomers by conventional methods, but it is also possible to use mixtures of isomers as photo-initiated species. Accordingly, the present invention also relates to mixtures of structural isomers of compounds of formulae I, II and III. According to the present invention, the compounds of the formulae I, II and III can be used as photoinitiators for photopolymerization of ethylenically unsaturated compounds or mixtures containing these compounds. Therefore 'another subject of the present invention is a photopolymerizable composition comprising: (a) at least one ethylenically unsaturated photopolymerizable compound; and (b) at least one of the chemical formulae I, η as defined above as a photoinitiator And / or III compounds. This composition may contain at least one further photoinitiator (c) and / or other additives in addition to the photoinitiator (b). The unsaturated compound (a) may contain one or more olefinic double bonds. It It can be low (monomer) or high (oligomer) molecular weight. Examples of monomers containing double bonds are alkyl, hydroxyalkyl or amine acrylates, or alkyl, hydroxyalkyl or amine groups Methyl acrylic acid, for example, methyl, ethyl, butyl, 2-ethylhexyl, or 2-hydroxyethyl acrylate, isobornyl acrylate, or methyl formaldehyde. Applicable to China National Standard (CNS) A4. (210X297mm) '34 _ (Please read the notes on the back before filling this page)

593357 A7 _____B7 _, _ V. Description of the invention (32) (Please read the notes on the back before filling out this page) Methyl methyl acrylate or ethyl methacrylate. Shi Xi_acrylate is also advantageous. Other examples are propionate, acrylamide, methacrylamide, ammonium, N-substituted (fluorenyl) acrylamide, vinyl esters (such as ethyl acetate), ethylene ethers (such as Isobutyl vinyl ether), styrene, alkyl- and halo-based styrene, N-vinylpyrrolidone, vinyl chloride or digas ethylene. Examples of monomers containing two or more double bonds are ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenol A and 4,4, -bis (2-propylene-fluorenyloxyethyl) (Oxy) diphenyl propane dipropionate, trisyl alcohol propionate triacrylate, pentaerythritol triacrylate or tetraacrylate, ethyl acrylate, monoethynylbenzene, diethynyl Polanic acid, glyme, diallyl phosphate, triallyl phosphate, triallyl mocyanurate or tris (2 • propenylethyl) isocyanurate. : Examples of relatively high molecular weight (aggregate) polyunsaturated compounds are acrylic epoxy resins, polyesters containing propionate-, ethylene- or epoxy-groups, and polyamines Carbamates and polyethers. Further examples of unsaturated polymerizers are unsaturated polyester resins, which are generally made from maleic acid, ugly acid, and one or more glycols, and have a molecular weight of about 500 to 3,000. In addition, vinyl ether monomers and oligomers, and maleic acid-terminated oligomers having polyacetate, polyurethane, polyether, polyvinyl ether, and epoxy backbones can also be used. It is particularly suitable as a polymer and a mixture of polymers with an ethylene ether group as described in WO 90/01512. However, copolymers of vinyl- and maleic-functional monomers are also suitable. Such unsaturated polymers can also be referred to as prepolymers. A particularly suitable example is Ethyl-Unsaturated Weak Acid and Polyols or Polyepoxy. This paper applies Chinese National Standard (CNS) A4 (210X297 mm). &Quot; ~ ^ 35I -593357 A7 _B7_ V. Description of the Invention ), And polymers with ethylene unsaturated groups in the chain or in the side groups, such as unsaturated polyesters, polyamines, and polyamines and their copolymers, containing ( (Meth) propylene-based polymers and copolymers, and mixtures of one or more of these polymers. Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, butenoic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic and methacrylic are preferred. Suitable polymers are aromatic and particularly aliphatic and cycloaliphatic polyols. Examples of the aromatic polyols are hydroquinone, 4,4'-dihydroxybiphenyl, 2,2-bis (4-based grain) propane, aging acid varnish and brewing resin a. Examples of polyepoxides are the above-mentioned polyols, especially aromatic polyols and epihydric alcohols. Other suitable polyols are polymers and copolymers containing a warp group in the polymer chain or in the side groups, especially polyvinyl alcohol and its copolymers or polyhydroxyalkyl methacrylate or its copolymers. A suitable further polyol is an oligoester having a base end group. Examples of aliphatic and cycloaliphatic polyols are preferably alkylene glycols having 2 to 12 carbon atoms, such as ethylene glycol, 丨, 2_ or 丨, 3_ propylene glycol, 1, 2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethanol, preferably from 200 to 150,000. Molecular weight of polyethylene glycol, U-cyclopentanediol, ... u or cyclohexanediol, 1,4-dimerylmethylcyclohexane, glycerol, tris (butylethyl) amine, trimethyl alcohol ethyl Hospital, trimethyl alcohol propane, pentaerythritol, dipentaerythritol and sorbitol. Polyols can be-acid or partially or completely with different unsaturated acid

., Order 丨 1 ·, 593357 A7 _____B7_ V. Description of the invention (34) The acetic acid is esterified, and in some esters, free hydroxyl groups can be modified, for example, by other acid bonding or § intent. Examples of esters are: dimethyl alcohol propane triacrylate, trimethyl alcohol propane triacrylate, trimethyl alcohol propane trimethacrylate, trimethyl alcohol propane trimethacrylate, tetrasex Methyl glycol difluorenyl acrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate Acrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octapropionate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate , Dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol triitaconate, dipentaerythritol pentaconate, dipentaerythritol Liuitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 13-butanediol dimethylpropane Isl S, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetramethacrylate, Sorbitol pentaacrylate, sorbitol hexaacrylate, oligomeric acrylates and fluorenyl acrylates, glyceryl diacrylates and triacrylates, 1,4-cyclohexane diacrylate, with 200 to 1 500 bis-acrylic acid and bis-methyl acrylic acid of knife 1 or a mixture thereof. Also suitable as component (a) is the same or different unsaturated carboxylic acid and this paper size applies Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297gongchu) 37 (Please read the back first (Please note this page and fill in this page again) • 、 可 |, 0m, A7 V. Description of the invention (35) Aromatic, cycloaliphatic and aliphatic polymers with 2 to 6 (especially 2 to 4) amino groups are preferred Amines of amines. Examples of these polyamines are ethylenediamine, stilbene, or propanediamine, 1,2_, 1,3-, or I; succindiamine, μ-pentanediamine, hexamethylenediamine, octanediamine, twelve Alkanediamine, 1,4-diaminocyclohexane, isophorone monoamine, phenylenediamine, bisphenylenediamine, diaminoethyl ether, dimethyltriamine, triphenylene Ethyltetramine, bis (/ 5-aminoethoxy)-or bis (cold-aminopropoxy) ethene. Other suitable polyamines are preferred to polymers and copolymers having additional amine groups in the side chain, and oligomeric amines having amine end groups. Examples of such unsaturated fluorenamines are fluorenyl bispropenamide, 1,6-hexamethylene bispropenamide, diethylene triamine trimethacrylamide, bis (methacrylamide) Propylpropoxy) ethane, y3-methacrylaminoethyl methacrylate, and N [(β-hydroxy-ethoxy) ethyl] acrylamido. Suitable unsaturated polyesters and polyamides are derived from, for example, maleic acid and derived from glycols or diamines. Some maleic acids can be substituted with other dicarboxylic acids. It can be used with ethylene unsaturated comonomers such as styrene. Polyesters and polyamides can also be derived from dicarboxylic acids and from ethylene unsaturated diols or diamines (especially those with relatively long chains, for example, 6 to 20 carbon atoms). Examples of the polyaminoacetic acid esters are composed of a saturated or unsaturated diisocyanate and an unsaturated or 'individually, saturated glycol. Polymers having (meth) acrylate groups at the side chain positions are also known. It may be, for example, the reaction product of a novolac-based epoxy resin with (meth) acrylic acid, or it may be a vinyl alcohol or its hydroxyalkyl derivative (which may be (enyl) endenoic acidified ) Homopolymer or copolymer, or may be (fluorenyl) acrylate (which can be esterified with hydroxyalkyl (meth) acrylate) 38 (Please read the precautions on the back before filling this page) This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) 593357 A7 B7 5. Homopolymer and copolymer of invention description (36). Other suitable polymer systems with acrylate or methacrylate groups in the side chain, for example, solvent-soluble or test-soluble polyimide precursors, for example, poly (fluorenate) compounds, which have Photopolymerizable side groups attached to the backbone or ester group in the molecule. These oligomers or polymers can be composed of novel photoinitiators and selective reactive diluents (such as polyfunctional (meth) acrylic acid esters) to prepare highly sensitive polyimide precursors Retardant. The photopolymerizable compound can be used alone or in any desired mixture. More preferably, a mixture of polyol (meth) acrylates is used. Examples of component (a) are also polymers or oligomers having at least divinyl unsaturated groups and at least one carboxyl functional group in the molecular structure, such as by using saturated or unsaturated polybasic anhydride and epoxy Compounds are obtained by reacting with the reaction products of unsaturated monocarboxylic acids, for example, photosensitive compounds described in JP 6-1638 and JP 10301276 and commercially available products such as EB9696, UCB Chemicals; KAYARAD TCR1025m Nippon Kayaku Co., LTD, Or an addition product formed between a carboxyl-containing resin and an unsaturated compound having an α, / 5-unsaturated double bond and an epoxy group (for example, ACA200M, Daicel Industries, Ltd.) 0 as a diluent, mono- or poly- A functional ethylenically unsaturated compound or a mixture of several of these compounds can be included in the above composition up to 70% by weight (based on the solid portion of the composition). The unsaturated compound (a) can also be used as a mixture with a non-photopolymerizable film-forming component. These can be, for example, physically dry polymers or their solutions in organic solvents, such as nitrocellulose or cellulose 39 (please read the precautions on the back before filling this page) This paper size applies to China Standard (CNS) A4 specification (210X297 mm) 593357 A7 B7 V. Description of the invention (37) (Please read the precautions on the back before filling this page) Acetyl butyrate. However, it may also be a chemical and / or thermally curable resin, such as polyisocyanate, polyepoxide, and melamine resins, and polyimide precursors. The simultaneous use of thermally curable resins is important for systems called hybrid systems, which are photopolymerized in the first stage and crosslinked by thermal post-treatment in the second stage. •, ^ τ— The present invention also provides a composition comprising at least one ethylenically unsaturated photopolymerizable compound as component (a), which is emulsified or dissolved in water. Many variations of these radiation-curable aqueous prepolymer dispersions are commercially available. The prepolymer dispersion is understood to be water and a dispersion of at least one prepolymer dispersed therein. The water concentration in this system is, for example, 5 to 80% by weight, particularly 30 to 60% by weight. The concentration of the radiation-curable prepolymer or prepolymer mixture is, for example, 95 to 20% by weight, particularly 70 to 40% by weight. In these compositions, the sum of the percentages shown for water and prepolymer is 100 'in each case, and adjuvants and additives can be added in varying amounts depending on the intended use. The radiation-curable, film-forming prepolymer dispersed in water and generally also dissolved is an aqueous prepolymer dispersion of a mono- or polyfunctional ethylene unsaturated prepolymer, which is known per se and can be obtained by free Radical initiation and having, for example, a content of polymerizable double bonds of 0.01 to 10 mol per 100 grams of the prepolymer system and, for example, an average of at least 400 (particularly 500 to 10,000) Molecular weight. However, higher molecular weight prepolymers can also be considered depending on the intended application. Use, for example, a polymer containing a polymerizable c_c double bond and an acid number of not more than 10, a polymer containing a polymerizable cc double bond, a polyepoxide containing at least two epoxide groups per molecule and at least one α, the radical-containing reaction product of chloro-ethylene unsaturated carboxylic acid, polyaminoacetic acid (former description (38)) acrylic acid ester and acrylic acid containing α, / 5-ethylenically unsaturated acrylic group Copolymer, as described in EP 12339. Mixtures of these prepolymers can be used similarly. Also suitable are the polymerizable prepolymers described in EP 33896, which have an average molecular weight of at least 600, a carboxyl content of 0.2 to 15%, and a range of 0.01 to 0.8 moles per 100 grams of prepolymer. Polymerization of thio-adducts of 1-in-1 prepolymers with double cc double bonds. Other suitable aqueous dispersions (mainly based on special alkyl (meth) acrylate polymers) are described in EP 41125, and suitable water-dispersible radiation-curable urethane acrylate prepolymers The substance can be found in DE 2936039. Further additives that can be included in these radiation-curable aqueous prepolymer dispersions are dispersion adjuvants, emulsifiers, antioxidants (eg, 2, thiothiobis (4_methyl_6_ tert-butyl) Phenol) or 2,6-di-tert-butylphenol), light stabilizers, dyes, pigments, fillers, such as glass or alumina, for example, talc, gypsum, silicic acid, rutile, carbon black, zinc oxide , Iron oxide, reaction accelerator, leveling agent, wetting agent, thickener, leveling agent, anti-foaming agent and other auxiliary agents commonly used in coating technology. A suitable dispersion adjuvant is a water-soluble organic compound having a high molecular weight and containing a polar group. Examples are polyvinyl alcohol, polyethylene-based fines, or cellulose fibers. Emulsifiers that can be used are nonionic emulsifiers, and if desired, ionic emulsifiers. In some cases, it is advantageous to use a mixture of two or more new photoinitiators. Of course, it is also possible to use a mixture with a known photoinitiator, such as a mixture with camphor, benzene, benzene, and benzene. Acetophenone, acetophenone derivatives, for example, 1-hydroxycycloalkylphenyl hydrazone or 2. meridyl-2-methyl. Phenyl-propanone, dioxoyl ethyl benzene, 593357 A7 ________B7_ V. Invention Explanation (39) α-Hydroxy- or α-aminoethylacetophenone, for example, (4 · fluorenylthiobenzyl) -1-amidino-1-morpholinylethane), 4-morpholine Benzamidine) -i-benzyl-1-dimethylaminopropane, 4-arylfluorenyl-1, dioxane, benzoin alkyl ether, and benzoyl ketal, such as dimethyl Benzophenone ketals, phenylglyoxylates and their derivatives, dimer phenylglyoxylates, diethylfluorenyl peresters, for example, benzophenone tetracarboxylic acid peresters as described in EP 126541 , Monofluorenylphosphine oxide, for example, (2,4,6 · trimethylbenzyl) diphenylphosphine oxide, bisfluorenylphosphine oxide, bis (2,6-difluorenyloxy) Benzamidine)-(2,4,4-trimethyl-phenyl) -phosphine oxide, bis (2,4,6-trimethylbenzyl) · phenylphosphine oxide, bis ( 2,4,6-trimethylbenzylidene) -2,4-dipentaoxophenylphosphine oxide, trimethylphosphine oxide, halomethyltriazine, for example, 2- [2- ( 4- Ethoxy-phenyl) -vinyl] -4,6-bis-trifluoromethyl- [1,3,5] triazine, 2- (4-methoxy · phenyl) -4,6- Bis-trifluoromethyl- [1,3,5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trifluoromethyl- [1,3,5 ] Triazine, 2-methyl-4,6-bis-trichloromethyl- [1,3,5] trifluorene, 2- (4-N, N-bis (ethoxycarbonylfluorenyl) amino) Phenyl) -4,6-bis (trifluoromethyl)-[1,3,5] triazine, 2- (4-fluorenyloxynaphthyl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (1,3-benzodioxane-5-yl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2- [4- (phenyloxy) phenyl] vinyl] -4,6 · bis-trifluoromethyl · Π, 3,5] triazine, 2- [2- (3-methyl -2-furyl) -vinyl] -4,6_bis-trifluoromethyl- [1,3,5] triazine, 2- [2- (5-fluorenyl-2-furyl) -ethylene Group] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2- (2,4-dimethoxy-phenyl) -vinyl] -4,6 -Bis-trichloromethyl- [1,3,5] triazine, 2- [2- (2-methoxy-phenyl) vinyl] -4,6-bis-trichlorofluorenyl- [1 , 3,5] triazine, 2- [2- [4-isopropoxy-phenyl] -vinyl] -4,6-bis-trigasmethyl- [1,3,5] triazine, 2- 42 (Please read Note on the back, please fill out this page again) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 593357 A7 ____B7_ V. Description of the invention (40) [2- (3-chloro-4-methoxy- Phenyl) vinyl] -4,6-bis-trigasmethane- [1,3,5] triazine, 2- [2 · Mo-4-N, N-:( ethoxycarbonylmethyl) amine -Phenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2-Ga-4-N, N-bis (ethoxy-carbonylmethyl) Amino-phenyl-4,6-bis-trichloromethyl_ [1,3,5] triazine, 2- [3-bromo-4, -N, N-«— (ethoxy &gt; Methyl) amino-phenyl] -4,6-bis-trifluoromethyl_ [1,3,5] trimethyl, 2- [3-Ga-4-N, N-di (ethoxy) Carbonylfluorenyl) amino-phenyl] -4,6-bis-dilactymethyl- [1,3,5] trione or, for example, G. Buhr, R.

Dammel and C. Lindley Polym. Mater. Sci. Eng. 61,269 (1989) and other halomethyl-triazines described in EP 0262788; halomethyloxazole photoinitiators such as US 4371606 and US As described in 4371607; 1,2-dimaple, such as described by EA Bartmann, Synthesis 5, 490 (1993); hexaarylbisimidazole and hexaarylbisimidazole / co-initiator systems, for example, with 2- M-benzobenzothiazole-bound o-hexahexaphenyl-bisimidazole, ferrocene cation compounds or titanocene, for example, bis (cyclopentadienyl) _bis (2,6-difluoro-3- Rotyl-phenyl) titanium. Although novel photoinitiators are used in hybrid systems, in addition to novel free radical hardeners, cationic photoinitiators, peroxide compounds, such as benzamyl peroxide (other suitable peroxides are described in the United States) Patent No. 4950581, 19th, 19th, 17-25), aromatic rhenium-, scale, or iodonium salt, as described in US Patent No. 5955581, 18th, 60th to 19th, 10th , Or a cyclopentadienyl-arene-iron (II) complex salt, for example, cumene) (β 5-cyclopentadienyl) -iron (II) hexafluorotannate, and oxime sulfonate Acid esters, such as those described in EP 780729. Furthermore, for example, pyridoxine and (iso) quinolinesulfonium salts described in EP 497531 and EP 441232 can be used in combination with novel photoinitiators. This paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) -43-J, M ......... (Please read the precautions on the back before filling this page) 5. Description of the invention ( 41) The novel photoinitiator (either alone or in combination with other known photoinitiators and photosensitizers) can also be used in the form of a dispersion or emulsion or aqueous solution made in water. The subject matter of the present invention is that the compound of formula I, II, in, iv or v contains at least one amino ketone (especially ('methylthiobenzyl) -1-amidino-1-morphine). Base). The photopolymerizable composition generally contains from 0.05 to 25% by weight (preferably from 0.001 to 10% by weight, especially from 0.01 to 5% by weight) of a photoinitiator (which is based on a solid composition as Benchmark meter). If an initiator mixture is used, this content is the sum of all photoinitiators added. Therefore, this content refers to the photoinitiator (b) or the photoinitiator (b) + (c). In addition to the photoinitiator, the photopolymerizable mixture may contain various additives (d). Examples are heat inhibitors, which are used to prevent premature polymerization, and examples are hydroquinones, hydroquinone derivatives, p-methoxyphenol, stone-naphthol, or sterically hindered phenols, such as 2,6_ Di-tertiary butyl · p-cresol. To increase storage stability in the dark, it may, for example, use copper compounds (for example, copper naphthenate, copper stearate or copper octoate), phosphorus compounds (for example, triphenylphosphine, dibutylphosphine, Triethylphosphite, triphenylphosphite, or tritylphosphite), quaternary compounds (e.g., tetramethylchloro chloride or trimethylbenzyl ammonium vapor or hydroxylamine Derivatives (eg, diethylhydroxylamine). To exclude atmospheric oxygen during the polymerization reaction, paraffin or similar wax-like substances can be added, which are inappropriately soluble in the polymer, and swim at the start of the polymerization reaction. Move to the surface and form a transparent surface layer to prevent air from entering. It is also possible to apply an oxygen-impermeable layer on the top of the coating, for example, poly (vinyl alcohol_) This paper size applies the Chinese national standard (Norway) A4 specification (21〇 χ297 public love) 593357 A7 _ B7 丨 '丨 丨 丨 丨 · 丨 .... V. Description of the invention (42) Co-vinyl acetate). Light stabilizers that can be added in small amounts are UV absorbers, such as hydroxybenzyl Benzotriazole, hydroxyphenyl_benzene Benzene, ammonium oxalate, or basic-s-disial type. These compounds can be used individually or in mixtures, and may or may not have hindered amines (HALS). These ultraviolet absorbers and light stabilizers Examples are 1. 2- (2'-Cyclophenyl) -benzyltriazole 4, for example, 2- (2'-Cyclo-5'-methylphenyl) benzotriazole, 2- (3 ', 5, -Di-Third-butyl_2, · hydroxyphenyl) benzobiazine, 2- (5 · Second-butyl-2'-acylphenyl) benzotria, 2- (2, -Ethyl-5-(1,1,3,3-tetramethylbutyl) phenyl) benzotrisine, 2- (3 ', 5'-di-third-butyl-2 '-Ethylphenyl) -5-chlorobenzotrifluorene, 2- (3-tertiarybutyl-2, -Ethyl-5'-fluorenylphenyl) -5-gasbenzotrifluorene, 2 -(3'-Second-butyl-5, -Third-butyl-2'-Ethylphenyl) benzotrisalazine, 2- (2'-Ethyl-4, -octyloxyphenyl) benzene Benzotriazole, 2- (3,5, -di-tertiarypentyl-2, · hydroxyphenyl) benzotriazole, 2- (3 ', 5'_bis (α, α-dimethyl) Benzyl) -2 '· hydroxyphenyl) benzotriazole, 2 · (3'-third butyl-2'-hydroxy-5,-(2-octyloxycarbonylethyl Group) phenyl) _5_chloro_benzotriazole, 2- (3, -third butyl-5,-[2- (2_ethyl-hexyloxy) -carbonylethyl] -2'- Hydroxyphenyl) -5-gas benzotriazole, 2- (3, -third butyl-2, · hydroxy-5 '· (2-methoxycarbonylethyl) phenyl) -5-chlorobenzene Benzotriazole, 2 (3, -Third-butyl-2'-hydroxy-5 '-(2-Methoxycarbonylethyl) phenyl) · benzotriazole, 2- (3, _Third-butyl -2, -hydroxy-5,-(2-octyloxy-carbonylethyl) phenyl) benzotriazole, 2- (3, -third butyl-5,-[2- (2-ethyl Hexyloxy) carbonylethyl] -2, -hydroxyphenyl) benzotriazole, 2- (3, -dodecyl-2, -hydroxy-5, -methylphenyl) benzotriazole and 2- (3, -Third-butyl-2, -hydroxy-5,-(2-isooctyloxycarbonylethyl) phenylbenzotriazole mixture, 2,2, -arylene-bis [ 4- (1,1,3,3-45 (Please read the notes on the back before filling in this page) This paper size is applicable to Chinese National Standard A4 (21〇 &gt; &lt; 297 mm) 593357 A7 __ _B7 5 2. Description of the invention (43) Tetrafluorenylbutyl) -6-benzotriazol-2-yl-phenol]; 2- [3, third butyl-5,-(2-fluorenyloxyethyl) ) -2'-Transyl-phenyl] -benzotrifluorene and transesterification product of polyethylene glycol 300; [R_CH2CH2-COO (CH2) 3] 2- where R is 3, -third butyl- 4'-Hydroxy-5, -2H-benzotriazol-2-yl-phenyl. 2. 2-Chrysene, such as 4-Chrysyl, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, Derivatives of 4,2,4, -trihydroxy and 2'-hydroxy-4,4'-dimethoxy. 1. Unsubstituted or substituted esters of jasmonic acid, such as 4-tert-butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoyl Resorcinol, bis (4-tert-butylphenylfluorenyl) resorcinol, benzoic acid, metabenzyl, 2,4-di-tert-butylphenyl 3,5-di- Tert-butyl-4 · hydroxybenzoate, cetyl 3,5-di-tert-butyl-4-hydroxybenzoate, stearyl 3,5-di-tert-butyl 4-hydroxybenzoate and 2-methyl-4,6-di-third-butylphenyl 3,5-di-third-butyl-4-hydroxybenzoate. Acrylates such as alpha-cyano- / 3, / 3-diphenyl isooctyl or ethyl ester, alpha-carbomethoxymethyl cinnamate, alpha-cyano-cold-methyl _ Butyl methoxycinnamate or methyl ester, α-carboxymethoxy-p-methoxycinnamate methyl ester and N- (Cold · Carbonoxy-Call-Cyanovinyl) _2_methyl ·. The bow is full. ^ ^ 1¾ amine 'for example, bis (2,2,6,6-tetramethyl-bromomethyl) sebacate, bis (2,2,6,6-tetramethyl-piperidyl) amber Acid ester, bis (1,2,2,6,6-pentamethylpyridyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidinyl) n-butyl- 3,5-mono-second butyl mesityl benzylmalonate, 1- mesityl_2,2,6,6- This paper size applies Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297 Gongchu) 46 (Please read the notes on the back before writing this page)

593357

Condensation products of tetramethyl-4-hydroxypiperidine and succinic acid, N, N, bis (2,2,6,6_tetramethyl-4-piperidinyl) hexamethylene diamine and 'third Condensation products of octylamino_2,6 · dichloro-1,3,5-s-diazine, tris (2,2,6,6-tetramethylpiperidinyl) azepine triacetate, Tetrakis (2,2,6,6-tetrafluorenyl) _4-piperidinyl) -12,3,4-butane tetraester, 1,1 '-(1,2_ethanediyl) _bis ( 3,3,5,5_tetrafluorenyl_piperazinone), 4-phenylfluorenyl-2,2,6,6_tetramethylpiperidine, 4 · stearyloxy_2,2,6 , 6_ tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidinyl) -2_n-methyl_2_ (2 · hydroxy-3,5-di-third-butyl Benzyl) malonate, 3-n-octyl_7,7,9,9_tetramethyl-1,3,8-diazaspiro [4,5] decane_2,4-dione Bis (1-octyloxy-2,2,6,6-tetramethylpiperidinyl) sebacate'bis (buoctyloxy_2,2,6,6_tetramethylpiperidinyl) Succinate, ^ &quot;, bis (2,2,6,6_tetrafluorenyl-4_piperidinyl) hexamethylene diamine and 4_morpholinyl-2,6_digas qj ,% Triazine condensation product, 2-gas-4,6-bis (4-n-butylamino group_2,2,6,6-tetramethylpiperidinyl) _ 1,3,5-diazine With 1 Condensation product of 2-bis (3-aminopropylamino) ethane, 2-chloro-4,6_bis (4-n-butylamino-1,2,2,6'-pentafluorenylpiperidine Group) condensation product of -1,3,5-triazine and 1,2-bis (3-aminopropyl) ethane, 8-ethenyl_3-dodecyl-7,7,9, 9-tetramethyl-i, 3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-fluorene- (2,2,6,6 · tetrafluorenyl -4-piperidinyl) pyrrolidone-2,5-dione and 3-dodecyl-1— (1,2,2,6,6-penta-methyl_4-piperidinyl) -pyrrole -2,5 · 2. Acetochlor, for example, 4,4, -dioctyloxypyrrolidine, 2,2, -diethoxypyrrolidine, 2,2, -di-octyloxy 5,5,- Di-Third-Butyloxadibenzidine, 2,2'-bis (dodecyloxy) -5,5, _Di-Third-Butyloxadibenzidine, 2-ethoxy-2'- Ethyl-acetoline, aniline, n, n, -bis (3-dimethylamine 47 ........... ί: "... · Fees: (Please read the precautions on the back before (Fill in this page)., May |, 0m, this paper size is applicable to Chinese national standard (CNS;) A4 specification (21〇 &gt; &lt; 297 public love) 593357 A7 ___ B7 5. Description of the invention (45) propyl propyl) Scopolamine, 2-ethoxy-5-tert-butyl-2, -ethylcuroxetidine and its relationship with 2-ethoxy-2'-ethyl-5,4, -di-third Mixtures of butylgrabentifen, mixtures of ortho- and para-fluorenoxy- and ortho- and para-ethoxy-disubstituted oxalopidine. 7.2- (2-Cycloylphenyl) -l, U-tris, such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl_1,3,5_tris Azine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4 -Dihydroxyphenyl) -4,6-bis (2,4-dimethyl) -1,3,5 · triazine, 2,4-bis (2-hydroxy-4 · propoxy_phenyl) -6- (2,4-Difluorenylphenyl) · 1,3,5-trihexyl, 2- (2-Cycloyl-4-octyloxyphenyl) -4,6_ (4-methyl · · Phenyl) -i, 3,5-triazine, 2- (2-hydroxy_4-dodecyloxybenzyl) -4,6-bis (2,4-dimethylphenyl) _1,3 , 5-triazine, 2- [2_hydroxy (2-hydroxy-3-butoxy-propoxy) phenyl, 4,6_bis (2,4_dimethylphenyl) _ 1,3 , 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propoxy) phenyl] _ 4,6-bis (2,4-dimethylphenyl) -i, 3, fluorenetrifluorene, 2_ [4_dodecyl_ / tridecyl-oxy- (2_hydroxypropyl) oxy_2-hydroxy-phenyl] _4,6_bis (2, 4-Dimethylphenyl) -1,3,5-trihexyl. I · Linosinites and phosphines_ "| ^, such as triphenylphosphite, diphenylalkylphosphite, Phenyldialkylphosphite, tris (nonylphenyl) Phosphite, dilaurylphosphite, tris (octadecyl) phosphite, distearyl-pentaerythritol phosphite, tris (2,4-di-tert-butylphenyl) phosphite , Diisodecyl pentaerythritol diphosphite, bis (2,4-di-third-butylphenyl) pentaerythritol diphosphite, bis (2,6-di_third-butyl_4_methylbenzene Based) pentaerythritol diphosphite, bis (isodecyloxy-pentaerythritol diphosphite), bis (2,4-di-tert-butyl winter methylphenyl) pentaerythritol diphosphine (please read the notes on the back first) (Fill in this page again)

The size of this paper is applicable to the national standard (CNS) A4 specification (21〇χ297 public directors) 48 593357 A7 ___ _ B7 V. Description of the invention (46) Salt filling, double- (2,4,6-three-third Butylphenyl) pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis (2,4-di · tertiary butylphenyl) -4,4'-bisphenylphenyl di Phosphite, 6-isooctyloxy_2,4,8,10_tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxocyclic ring ( dioxaphosphocine), 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl. dibenzo [(11] -1,3,2-dioxophosphate heterocyclic ring, bis ( 2,4-di-tertiary-butyl-6-methylphenyl) methyl phosphite and bis (2,4-di-tertiary-butyl-6-fluorenylphenyl) ethyl phosphite. To accelerate the polymerization reaction, amines can be added as component (d), for example, triethanolamine, N-methyldiethanolamine, ethyl-p-dimethylaminophenylbenzoate, 2-('-methylamine ) Ethylbenzate, 2-ethylhexyl-p-dimethylaminobenzoate, octyl-p-N, N-dimethylaminobenzoate, NJ2-hydroxyethyl ) -N-methyl-p-toluidine or Michler Michler) ketone. The effect of amines can be enhanced by the addition of aromatic ketones of the benzophenone type. Examples of amines which can be used as oxygen scavengers are substituted N, N-dialkylanilines as described in EP 339841. Other accelerators, co-initiators and adjuvants are thiols, thioethers, disulfides, scale salts, phosphine oxides or phosphines, for example as described in EP 438123, GB 2180358 and JP Kokai Hei 6-68309. It is further possible to add a conventional chain transfer agent in the art to the composition according to the present invention as component (d). Examples are thiols, amines and benzothiazoles. The photopolymerization reaction can also be accelerated by adding further photosensitizers or co-initiators (as component (d), which shifts or broadens the spectral sensitivity). Especially aromatic compounds, such as benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, coumarin and phenothiazine and its derivatives, this paper size applies to Chinese national standards (CNS) A4 specifications (210 X 297 mm) 49 (Please read the precautions on the back before filling out this page). Order ·-豢-593357 A7 ______ B7 V. Description of the invention (47) &quot; ~ — — and 3 -(Arylmethyl) sialylline, rhodanine, clavulanic acid, and eosin, rhodamine, erythrosine sodium salt, glutathione, thioxanthin, acridine, for example, 9-phenyl Mouth yam, 1,7-bis (9K-based) heptyl, W-bis (9m) pentane, cyanine and cyanine dye. Specific examples of these compounds are: 1. Oral ketone_ thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, chloro-cardiopropoxythioxanthone, 2-dodecane Thiothioxanthone, 2, 'diethylthioxanthone, 2,' dimethylthioxanthone, 1-methoxy-carbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3- (2 -Methoxyethoxycarbonyl &gt; thioxanthone, 'butoxycarbonylthioxanthone_, 3-butoxycarbonyl-7-methylthioxanthone, cyano-3_airthioxanthone, Ethoxycarbonyl-3-chlorothioxanthone, 丨 _ethoxycarbonyl-3_ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone_, 丨 -ethoxycarbonylbenzene Thiothioxanthone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonylthioxanthone, 1,3-dimethyl-2-meryl-9HH9- Ketone 2-ethylhexyl ether, 1-ethoxycarbonyl-3- (1-methyl_1_morpholinylethyl) &gt; thioxanthone, 2.methyl-6-dimethoxymethyl- Thioxanthone, 2-methyl-6- (1,1-dimethoxybenzylthioxanthone, 2-morpholinylmethylthioxanthone, 2-methyl-6-morpholinylmethyl Thioxanthone, N-allyl thioxanthone-3,4-dicarboxyfluorenimine, N_octyl thioxanthone_3,4_dicarboxylic acid Imine, N- (l, l, 3,3-tetramethylbutylthioxanthone-3,4ι_dicarboxyfluorenimine, 1-phenoxythioxanthone, 6-ethoxycarbonyl_2 _Methoxythioxanthone, 6_ethoxycarbonyl-2_methylthioxanthone, thioxanthene carboxylic acid polyethylene glycol ester, 2-hydroxy-3- (3,4-dimethyl_9 _Oxygen · 9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanyl chloride. --------This paper size applies to Chinese national standards (⑽ ) A4 specifications (21〇 &lt; 297 public love) -50-

、 一 t—: line 丨 (Please read the precautions on the back before filling this page) 593357 A7 _____B7_ V. Description of the invention (48) Oxybenzylbenzene, 4,4, -dimethoxybenzylbenzene, 4,4'-dimethylbenzylbenzene, 4,4, digas benzylbenzene, 4,4, -bis (difluorene) Aminoamino) phenylbenzene, 4,4'-bis (diethylamino) phenylbenzene, 4,4, -bis (methylethylamino) phenylbenzene, 4,4, -bis ( P-Isopropylphenoxy) phenylbenzene, 4-fluorenylbenzene, benzene, 2,4,6-trimethyl-benzene, benzene, 4- (4-methylthiophenyl) -benzene, Benzene, 3,3'-difluorenyl-4-methoxyphenylhydrazine, fluorenyl_2-phenylfluorenylbenzoate, 4- (2-hydroxyethylthio) -phenylhydrazine, 4_ (4_fluorenylthio) -phenylhydrazine, 1- [4- (4-benzylfluorenyl-phenylsulfanyl) _phenylbenzene 2-fluorenyl-2- (fluorenyl-4 -Shi Huanghuangji) propan-1-vinyl |, 4-phenylfluorenyl-N, N, N-trimethylphenylbenzyl chloride, 2-hydroxy-3_ (benzylidenephenoxy) -N, N, N-trimethyl-1-propaneammonium gaseous monohydrate, 4- (13-propenyl- 1,4-, 7,10,13-pentatridecyl)- Phenylbenzene, 4-benzylamino- 1 ^ -diamidyl-N- [2 · (1-oxo-2-propenyl) oxy] ethyl-phenylphosphonium ammonium gasification; 3. Coumarin Coumarin, Coumarin 2, Coumarin 6, Coumarin 7, Coumarin 30, Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337, Coumarin 500, 3-Phenylcoumarin, 3-Phenyl-7-methyl Oxycoumarin 1, 3-phenylfluorenyl-5,7-dimethoxycoumarin, 3-phenylfluorenyl-5,7-dipropoxycoumarin, 3-benzidine 6-6,8-dichlorocoumarin 1, 3-phenylfluorenyl-6-chloro-coumarin, 3,3'-carbonyl-bis [5,7-bis (propoxy) -coumarin ], 3,3'-carbonyl-bis (7-methoxycoumarin), 3,3'-carbonyl-bis (7-diethylamino-coumarin), 3-isobutylammonium coumarin Plain, 3- This paper size applies to Chinese national standards (CNS> Α4 size (210X297 mm) 51 (Please read the precautions on the back before filling this page), OK | 593357 A7

Benzamyl, 5,7-dimethoxy-coumarin, 3-benzyl, 5,7_diethoxy-coumarin, 3-benzyl-5,7-di Butoxycoumarin, 3-benzylidene-5,7-bis (methoxyethoxy) -coumarin, 3-benzylidene) _5,7-bis (allyloxy) Coumarin, 3-benzylidene-7-dimethylaminocoumarin, 3-benzylidene-7-diethylaminocoumarin, isobutyryldimethylaminocoumarin , 5,7-dimethoxy-3- (1-naphthyl) -coumarin, 5,7 • diethoxy-3- (1-naphthyl) -coumarin, 3- Benzamylbenzo [f] coumarin, 7_diethylamino-3-thienylcoumarin, 3- (4-cyanobenzyl) &gt; 5,7_dimethyl Oxycoumarin, 3- (4-cyanobenzyl) _5,7_dipropoxycoumarin, 7-difluorenylamino · 3-phenylcoumarin, 7-diethyl Aminoamino-3-phenylcoumarin, coumarin derivatives disclosed in JP 09-179299-A and JP 09-325209-A, for example, 7-[{4-chloro-6- (diethyl Methylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin; 4. 3- (arylfluorenylmethyloxazolyl 3-methyl-2-benzidine Methylendaline-naphthalene -Benzylidene-methylphenyl-benzylidene, 3-ethyl-2 -propylidenemethylidene_stone_naphthothiazoline; 5. rhodanine 4-dimethylaminophenylidene rhodanyl Ning, 4-diethylaminobenzylidene rhodanine, 3 -ethyl-5 (3-octyl-2-benzoxanthenylidene)-rhodanine, jp 08-305019A Rotanin derivatives, chemical formulas [1], [2] ,; 6. Other compounds acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzoin, 4,4 ' -Bis (dimethylamino) benzidine, 2-ethenylnaphthalene, 2-naphthaldehyde, danshen 52 (Please read the notes on the back before filling this page) •, tr — fee-paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) Description of the invention (50) Sour bamboo bio, 9,10-anthracene, anthracene, you, amine, phenanthrene, phenanthrene, phenanthrene, 9-benzene, 9-benzene Acylcycloheptanone, curcumin, glutanone, thiomichelone, α- (4-diamidoaminophenylidene) ketone, for example, 2,5-bis (4-diethylamino) Phenylidene) cyclopentanone, 2- (4-dimethylamino-phenylidene) _indane_ 丨 _one, 3_ (cardiodimethylamino-phenyl) -1-indane-5 -Base-C Enone, 3-phenylthiophthalimide, imine, N-fluorenyl-3,5-bis (ethylthio) _ugenimine, N-fluorenyl_3 5_bis (ethylthio) -Phthalimide, phenothiazine, methylphenothiazine, amino groups, for example, N-phenylglycine, ethyl 4-diamidinoaminobenzoate, butoxyethyl 4-dimethyl Aminoamino benzoate, p-dimethylaminoacetanilide, triethanolamine, methyldiethanolamine, dimethylaminoethanol, 2- (dimethylamino) ethylbenzoate, poly ( Propylene glycol) 4- (difluorenylamino) benzoate. Photosensitive compounds containing as further additives (d) a group selected from the group consisting of benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives or coumarin derivatives The polymerization composition is preferred. The curing method can be assisted by the addition of photosensitizers, especially for compositions that are colored (for example, titanium dioxide), and can also be added by components that form free radicals under thermal conditions (for example, azo compounds, Such as 2,2, _Azobis (4-methoxy-2,4-dimethylvaleronitrile), triazene, diazosulfide, pentaazadiene or peroxide, for example, peroxide Hydrogen or peroxycarbonate, for example, tert-butyl hydroperoxide, for example as described in EP 245639). The composition according to the present invention may contain as a further additive (for example, photoreducible dyes, for example, gutton, benzoxanthan ... benzothiaxanthen, 593357 A7 _ B7 5. Description of the invention (51) thiazine _, Paronin_, porphyrin- or acridine dyes and / or trichonyl methyl compounds, which can be cleaved by radiation. Similar composition systems, for example, are described in Ep 445624. Further additives known in the art Can be added as component (d), for example, flow improver, adhesion promoter, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane , N- (2-aminoethyl) _3-aminopropylmethyldimethoxysilane, n_ (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3.aminopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethylmethyldimethoxysilane, chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Alkanes and sulfonyl propyltrimethoxy stone sintered. Surfactants, photointensifiers, colorants, dyes, wetting agents, leveling aids, dispersants, coalescence preventers, antioxidants or fillers Further examples of additives (d). For curing thick and colored coatings, glass microspheres or broken glass fibers are suitably added, as described in US 5013768. The choice of additives (d) depends on the application field and this field The required properties are this. The above additives are commonly used in this technology, so they are added at the usual levels in individual applications. '着 W] can also be added to this novel composition. This is when the photopolymerizable compound is a liquid or viscous substance Is particularly advantageous. The amount of the adhesive is, for example, 2 to 98% by weight (preferably 5 to 95% by weight, and particularly 20 to 90% by weight, which is relative to the overall solids content). The selection is based on the application of this paper. The size of the Chinese A4 standard is 297 mm.

— (Please read the notes on the back before filling this page) tr 丨 593357 A7 B7 V. Description of the invention (52) The field and the properties required in this field are 'such as developing ability in aqueous and organic solvent systems, Substrate adhesion and sensitivity to oxygen. Examples of suitable adhesives are polymers having a molecular weight of about 2,000 to 2,000,000 (preferably 5,000 to 1,000,000). Examples of alkaline developable adhesives are propylene polymers having carboxylic acid functionality as a pendant group, such as conventionally known by ethylene unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (Meth) acrylic acid, 2-carboxypropyl (meth) acrylic acid, itaconic acid, butenoic acid, maleic acid, fumaric acid, and ω-carboxy polycaprolactone mono (methacrylate)) and one or More selected from esters of (meth) acrylic acid (such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) propionate, butyl (meth) acrylate, Benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (fluorenyl) acrylate, Tricyclic [5 · 2 · 1 · 〇2.6] dec-8-based (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3 , 4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (fluorenyl) acrylate); vinyl aromatic compounds (E.g., styrene, α-methylphenethylhydrazone, ethyl acetophenone, p-chloroacetophenone, vinylbenzyl glycidyl ether); ethylamine unsaturated compounds, (meth) propylene Diamine diacetone acrylamide, N-methyl alcohol propylamidine, N-butoxy methacrylamide; and polyolefin-based compounds (such as butyl butyrate, isoamidine, SL Dingfu etc.); Meprofen, methylisopropenone, mono-2-[(fluorenyl) propenyloxy] ethyl succinate, phenylmaleimide, maleic acid Sf, ethyl acetate, ethyl propionate, vinyl valerate, polystyrene macromonomer, or poly (meth) acrylate giant mono 55 m I ........... ............ 4IW— (Please read the precautions on the back before filling this page). Order — — Mongolia — This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 593357 A7 _— _B7_ V. Copolymer obtained by copolymerization of monomers of the invention (53). Examples of copolymers are copolymers of acrylic acid vinegar and methacrylic acid esters with acrylic acid or methacrylic acid and with styrene or substituted styrene, phenolic resins (for example, novolac), (poly) warp-based styrene, and Copolymer of hydroxystyrene with alkyl acrylate, acrylic acid and / or methacrylic acid. Preferred examples of the copolymer are a copolymer of methyl methacrylate / methacrylic acid, a copolymer of benzyl methacrylate / methacrylic acid, a copolymer of methyl methacrylate / ethyl acrylate / methacrylic acid Copolymer of phenylmethyl methacrylate / methacrylate / styrene, copolymer of benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate, methyl methacrylate / butyl methacrylate Ester / Methylpropionic Acid / Styrene Copolymer, Methacrylic Acid Methyl Acetate / Methyl Acrylate Methyl Acrylate / Methacrylic Acid / Hydroxyphenyl Acrylic Acid Copolymer. Examples of solvent developable adhesive polymers are poly (alkyl fluorenyl acrylate), poly (alkyl acrylate), poly (benzyl methacrylate_co-fluorenyl hydroxyethyl acrylate · co-methyl Acrylic acid), poly (benzyl acrylate-co-methacrylic acid); cellulose esters and cellulose ethers (such as cellulose acetate, cellulose acetobutyrate, ethyl cellulose, ethyl Cellulose); polyvinyl butyral, polyvinyl methylal, cyclized rubber; polyethers (such as polyethylene oxide, polypropylene oxide, and polytetrahydrofuran); polystyrene, polycarbonate, Polyurethanes, Polyolefins, Polyolefins, Polyethylene, Polyvinyl Chloride / Vinylidene Copolymer, Vinylidene Vinyl and Propylene Resin, Copolymers of Ethyl Acrylate and Vinyl Acetate, Polyvinyl Acetate Esters, copolymers (ethylene / vinyl acetate), polymers such as polycaprolactam and poly (hexamethylene adipamide), and poly (ethylene glycol terephthalate) and poly ( Six basic dimensions of the paper are applicable to China National Standard (CNS) A4 (210X297 Mm) 56 (Please read the notes on the back before filling out this page) Order ·-Fees-593357 A7 I —--------! Z_____ V. Description of the Invention (54) &quot; ~ '~' Monodiol Succinate) polymer and polyimide adhesive resin. The polyimide adhesive resin in the present invention may be a polyimide or a polyimide precursor suitable for a solvent, for example, poly (amidate). I is preferably a photopolymerizable composition comprising a methacrylic acid ester as a binder polymer (e) and a copolymer of methacrylic acid. Further interested parties are, for example, the polymer adhesive component described in JP 1 (M7111, A, especially for color filters. The photopolymerizable composition can be used for various purposes, for example, as a printing ink ( For example, screen printing inks, offset printing or offset printing inks), as a smooth finish, as a white or color finish (for example, for wood or metal), as a powder coating, as a coating material (for Paper, metal or plastic, etc.), as light-curable coatings for building markings and road markings, for photocopying technology, for holographic recording materials, for image recording technology, or for making printing plates (which It can be developed with organic solvents or alkaline aqueous solution), used as a mask for screen printing, as a dental filling composition, as an adhesive, as a pressure-sensitive adhesive, as a laminating resin, as an etching resist, as a solder resist. Agents, plating resists, or permanent resists (liquid and dry film) as photo-constructible dielectrics (eg, printed circuit boards and electronic circuits) as Preparation of color filters for various display applications or resists that produce structures in the production methods of plasma · display panels and electroluminescent displays (eg, US 5853446, EP 863534, JP 09-244230-A, JP ι〇 · 62980 · Α, jP 08_171863_ A, US 5840465, EP 855731, jp 〇5_271576-A, JP 05-67405-A), used to prepare optical switches, optical lattices (interference lattices), photoelectric books The paper size applies the Chinese National Standard (CNS) A4 specification (210X297)-~ 57— &quot;----

---- (Please read the precautions on the back before filling in this page). Ⅰ-T— Fee 593357 A7 _B7_ 5. Description of the invention (55) Road for curing by the body (UV curing in transparent mold) ) Or by using three-dimensional lithography to produce three-dimensional objects, such as described in US 4575330, composite materials (for example, styrenic polyester, if desired, may contain glass fibers and / or other fibers and other adjuvants) and other thick Layer composition for coating or sealing electronic components and integrated circuits, or as a coating for optical fibers, or for making optical lenses, such as contact lenses or Fresnel lenses. The composition according to the invention is further suitable for preparing medical devices, adjuvants or implants. Furthermore, the composition according to the invention is suitable for the preparation of gels with directional thermal properties, for example as described in DE 19700064 and EP 678534. This novel composition can additionally be used as an initiator for emulsion polymerization, granular polymerization or suspension polymerization, a sequential polymerization initiator that fixes liquid crystal monomers and oligomers, or as an initiator for dye fixation on organic materials. Agent. In the coating material, a mixture of a prepolymer and a polyunsaturated monomer is generally used, which may additionally contain a monounsaturated monomer. The prepolymers here mainly specify the properties of the coating film, and by changing them, those skilled in the art can influence the properties of the cured film. The polyunsaturated monosystem acts as a cross-linking agent, which makes the film insoluble. Monounsaturated monomers are used as reactive diluents and are used to reduce viscosity without the use of solvents. Polyester resins are generally used in two-component systems with monounsaturated monomers, preferably styrene. For photoresist, a special one-component system is generally used, for example, polymaleimide, polyarylpropylene, arene or polyimide, as described in DE 2308830. The novel photoinitiator and its mixture can also be used for radiation curable powder. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 58 ------- r! 0 ^ —— (Please read first Note on the back, please fill out this page again) •, OK | 593357 A7 _____B7 _ V. Description of the invention (56) Polymerization of the coating. The powder coating may be mainly a solid resin and a monomer containing a reactive double bond (for example, maleate, vinyl ether, acrylate, acrylamide, and mixtures thereof). Free radical UV-curable powder coatings can be formulated by mixing an unsaturated polyester resin with acrylamide (eg, amidinofluorenyl propyleneamine aminoglycolate) and a novel free radical photoinitiator. These compositions are described in, for example, thesis, "Radiation Curing of Powder Coatings" "Conference Proceedings, Radtech Europe 1993" M. Wittig and Th. Gohmann. Powder coatings may also contain adhesives, for example, DE 4228514 and EP 636669. Free radical UV curable powder coatings can also be prepared by mixing unsaturated polyesters with solid acrylates, methacrylates or vinyl ethers and novel photoinitiators (or photoinitiators Powder mixture). Powder coatings may also contain adhesives, for example as described in DE 4228514 and EP 636669. UV-curable powder coatings may additionally include white or colored pigments. For example, preferably, Rutile titanium oxide can be used at a concentration of up to 50% by weight to produce a solid powder coating with good hiding power. This procedure generally involves subjecting the powder to static electricity or friction Electrically sprayed on a substrate (for example, metal or wood), melted the powder by heating, and used after the formation of a smooth film, such as a medium-pressure mercury lamp, metal toothed lamp or xenon lamp with UV and / Or visible light radiation to cure this coating. The special advantage of radiation curable powder coating over its thermal curing is that the flow time of powder particles can be delayed to ensure smooth high gloss coating. In contrast to heat-curable systems, radiation-curable powder coatings can be formulated to melt at lower temperatures without undesired effects of shortening their life. Because 59 (please read the note on the back first Please fill in this page for further details.) This paper size applies the Chinese national standard A4 specification (21〇 &lt; 297 mm> 593357 A7 B7. 5. Description of the invention (57 This is also suitable as a heat-sensitive substrate (for example, wood or Plastic) coatings. In addition to the novel photoinitiator system, this powder coating composition can also contain UV absorbers. Suitable examples are listed in paragraphs 1-8 above. This novel photocurable The composition is suitable, for example, as all kinds of substrates (for example, wood, fabric, paper, ceramic, glass, plastic, such as polyester, polyethylene terephthalate, polyolefin, or cellulose acetate 'Especially in the form of thin films, and coating materials such as A1, Cu, Ni, Fe, Mg or Co and GaAs, Si or SiOJ, the substrate is to be coated with a protective layer, or by imaging The new radiation-sensitive composition is further found to be used as a negative photoresist, which has a very high sensitivity to light and can be developed in aqueous alkaline media without expansion. It is suitable for preparation for use in Printing molds or screen printing molds for letterpress, lithography, and gravure printing, for the production of letterpress printing copies, for example, for the preparation of braille characters, for stamps, for chemical resistance, or for micro-resistance for integrated circuits Agent. This composition further serves as a dielectric layer or coating that can be patterned by light, and is used as an embedding material and isolation coating for the production of computer chips, printed circuit boards, and other electrical or electronic components. Possible layer support and coating substrate processing conditions may vary. The novel composition also relates to a photosensitive thermosetting resin composition and a method for forming a solder resist pattern by using the same, and more particularly, it relates to a method for preparing printed circuit boards, precision preparation of metal objects, and etching of glass and stone objects. , A novel photosensitive thermosetting resin composition for embossing of plastic objects and materials for preparing printed boards, especially as a solder resist for printed circuit boards, and by selectively passing the resin composition layer through a patterned substrate Yu Bujingzhi ................. r! 0 ^ …… (Please read the notes on the back before filling out this page), OK |. Fee-This paper size applies Chinese national standards ( CNS) A4 specification ⑵〇χ297 公 爱) A7 -------- B7_ V. Description of the invention (58) &quot; ~ &quot;--Exposure of actinic ray of photomask and unexposed part of this layer A method for forming a solder resist pattern in steps such as development. A solder resist is a substance that is used during soldering of a specific portion to a printed circuit board to prevent molten solder from adhering to irrelevant portions and to protect the circuit. Therefore, it is necessary to possess properties such as high adhesion, insulation resistance, soldering temperature resistance, solvent resistance, alkali resistance, acid resistance, and plating resistance. Since the photocurable composition according to the present invention has good thermal stability and is sufficiently resistant to the inhibition by oxygen, it is particularly suitable for preparing color filters or color mosaic systems, such as those described in Ep 32〇264. Described. Color filters are generally used to prepare LCDs, projection systems, and image sensors. Color filters can also be used, for example, in television receivers, video monitors or computer monitors and image scanners, flat display technology, etc. The decanter is generally made by forming red, green, and blue pixels and a black matrix on a glass substrate. In these methods, the photocurable composition according to the present invention can be used. A particularly preferred method of use includes adding red, green, and blue color materials, dyes, and colorants to the photosensitive resin composition of the present invention, coating the substrate with the composition, and drying the coating with a short heat treatment to make the The coating is exposed to actinic radiation in a patterned manner, and thereafter the pattern is developed and selectively heat treated in an aqueous developer solution. Therefore, by subsequently applying green and blue coatings on top of each other in this order in this method, a color filter layer with red, green, and blue pixels can be produced. Development is accomplished by washing away areas that have not been polymerized with a suitable diagnostic developing solution. This method is repeated to form an image with several colors. In the photosensitive resin composition of the present invention, there is at least one or 61 in between (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (59) A method in which more pixels are formed on a transparent substrate and then exposed from one side of the transparent substrate (the side on which the above-mentioned pixels are not formed), and the above-mentioned pixels can be used as a light-shielding mask. In this case, for example, in the case where an overall exposure is applied, the adjustment of the mask position is not required and the consideration of its position slip is removed. And, all the portions on which the above-mentioned pixels are not formed can be cured. Moreover, in this case, it is also possible to develop and remove a part where the above-mentioned pixels are not formed by using a partial hood. Since no gap is formed between the pixels formed before and after in any case, the composition of the present invention is suitable for, for example, forming materials for filters and color filters. Specifically, red, green, and blue color materials, dyes, and color materials are added to the photosensitive resin composition of the present invention, and the image forming U method is repeated to form red, 4, and blue pixels. Then, for example, a photosensitive resin composition to which a black overtone material, a dye, and a colorant are added is provided on the entire surface. Holistic exposure (or partial exposure through a hood) provides black pixels on all spaces (or all except a portion of the hood) between red, green, and blue pixels. In addition to the method in which the photosensitive resin composition is coated on a substrate and dried, the photosensitive resin composition of the present invention can also be used as a layer transfer material. That is, the photosensitive resin composition is directly provided in a layer form on a temporary support, preferably on a polyethylene terephthalate film, or an oxygen shielding layer and a chlorine ionization layer or a release layer are provided thereon. And an oxygen shielding layer is provided on the polyethylene terephthalate film. Generally, a removable cover sheet made of synthetic resin is laminated thereon to provide protection during processing. Furthermore, an alkali-soluble thermoplastic resin layer and an intermediate layer may be applied on the temporary support 593357 A7 B7 5. The layer structure of the invention description (60), and further, a photosensitive resin composition layer Provided thereon (JP 5-173320-A) ° The above cover sheet is removed at the time of use and the photosensitive resin composition is laminated on the permanent support. Thereafter, when the oxygen shielding layer and the peeling layer are provided, the peeling effect is performed between these layers and the temporary support, and when the peeling layer and the oxygen shielding layer are provided, the peeling effect is performed between the peeling layer and the oxygen shielding layer. When the release layer or the oxygen shielding layer is not provided, the peeling effect is performed between the temporary support and the photosensitive resin composition, and the temporary support is removed. Metal supports, glass, ceramics, and synthetic resin films can be used as supports for color filters. Glass and synthetic resin films that are transparent and have excellent dimensional stability are particularly preferred. The thickness of the photosensitive resin composition is generally 0.1 to 50 m, particularly 0.5 to 5 m. If the composition contains an alkali-soluble resin or an alkali-soluble monomer or oligomer, a dilute aqueous solution of an alkaline substance can be used as a developing solution for the photosensitive resin composition of the present invention. A developer solution prepared by mixing organic solvents may also be included.

Examples of suitable alkali materials include alkali metal hydroxides (for example, sodium hydroxide and potassium hydroxide), metal test salts (for example, sodium carbonate and potassium carbonate), metal test bicarbonates (for example, sodium bicarbonate and Bicarbonate clock), metal silicates (for example, sodium and potassium silicate), alkali metal metasilicates (for example, sodium and potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine , Morpholine, tetraalkylammonium hydroxide (for example, tetramethylammonium hydroxide), or trisodium phosphate. The concentration of alkali substances is 0.01 to 30% by weight, and pH 63 (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 3357 A7 _ — —___ B7 V. Invention Description (61) Preferably 8 to 14. Suitable organic solvents that can be mixed with water include methanol, ethanol, 2-propanol, propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono-n-butyl alcohol. Butyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, n-butylethyl Acid ester, benzyl alcohol, acetone, methyl ethyl hydrazone, cyclopentanone, cyclohexanone, 2-heptanone, 2-pentanone, ε-caprolactone, γ-butyrolactone, monomethyl Formamidine, dimethylacetamide, hexamethylphosphamide, ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of the organic solvent miscible with water is from 0.1 to 30% by weight. Furthermore, publicly known surfactants may be added. The concentration of the surfactant is preferably 0.001 to 10% by weight. The photosensitive resin composition of the present invention can also be developed with an organic solvent, and contains a blend of one or more solvents, but does not contain a test compound. Suitable solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, Diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, fluorenyl-3-methoxypropionate, n-butyl acetate, benzene Methyl alcohol, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 2-pentanone, ε-caprolactone, butyrolactone, dimethylphosphonium, dimethyl Acetylamine, hexamethylphosphoramide, ethyl lactate, fluorenyl lactate, ε-caprolactam and N-methylpyrrolidone. Alternatively, water can be added to these baths to the extent that a clear solution can still be obtained and sufficient solubility of the unexposed areas of the photosensitive composition is maintained. 64 (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standards (CNS) A4 specification (210X297 public love) 593357 A7 ____B7_ 5. Description of the invention (62) Developer solution can be familiar with this It is used in all forms known to the skilled person, for example, in the form of a batch solution, a kneading or spraying solution. To remove the uncured portion of the photosensitive resin composition, these methods can be combined, such as wiping and rotating brushing, and wiping with wet sponge. Generally, the temperature of the developing solution is preferably from room temperature and its vicinity to 40 ° C. The development time may vary depending on the specific type of photosensitive resin composition, the testability and temperature of the developing solution, and the type and concentration of the organic solvent when the organic solution is added. It usually takes 10 seconds to 2 minutes. A washing step may be applied after the development process. The final heat treatment is preferably performed after the development treatment. Therefore, a support having a layer that can be photopolymerized by exposure (hereinafter referred to as a photocurable layer) is heated in an electric furnace and a dryer, or the photocurable layer is irradiated with an infrared lamp or heated on a hot plate. The heating temperature and time depend on the composition used and the thickness of the formed layer. Generally, the heating is preferably performed at about 12 (rc to about 25 ° &lt; t for about $ to about 60 minutes. Colors that can be included in the composition according to the present invention (including the color filter composition) The material is preferably a color material to be processed, for example, by finely dispersing the color material in at least one selected from the group consisting of acrylic resin, chloroacetic acid, acetic acid copolymer, maleic acid resin, and ethyl cellulose resin. A powdery or pasty product made by the tree of the group that is formed within a month. Red pigments include, for example, anthraquinone-type pigments alone, fluorene-type pigments alone, or at least one and two of them Nitrogen-based yellow colorant or heterodihydrogen nozzle-colored colorant mixture, especially separately &lt; c · ι. Red colorant alone C. I. Red colorant 155 or by At least one yuan of nc · I · red colorant 155 and c · J · yellow colorant 83 or c · | · 5 scales are suitable (Please read the precautions on the back before filling this page)

Can I 593357

V. Description of the invention (63) A mixture of yellow pigments 139 ("C I •" refers to the color index, which is known to those skilled in the art and is publicly available). Further suitable examples of the colorant are c · I · red colorant 105, 144, 149, 176, 177, 185, 202, 209, 214, 222, 242, 254, 255, 264, 272, and CI yellow colorant 24 , 31, 53, 83, 93, 95, 109, 110, 12m9, 138, 139, 166 and C.I. Orange Pigment 43. The green colorant includes, for example, a separate phthalocyanine type colorant or a mixture thereof with a diazo-type yellow colorant or an isodihydroindipure-type yellow colorant, especially a C · I · green colorant alone 7. Separate c · j · green color material 36, Separate C · I · green color material 37 or c · I. Green color material 7, c ·; [.Green color material 36, C. I · green color Material 37, a mixture of at least one element of C.I. green colorant 136 and CI yellow colorant 83 or C.I. yellow colorant 139. Other suitable green pigments are C · I · green pigments 15 and 25. Examples of suitable blue colorants are phthalocyanine-type colorants, which are used alone or in combination with diazoline-type purple colorants, for example, c · I · blue color 15: 3 and C · I · purple color 23 mixture. Further examples of the blue pigment are c j blue 15: 3, 15: 4, 15: 6, 16 and 60, that is, phthalocyanine C I blue pigment 15: 3 'or Dicyan C.I. blue pigment 15: 6. Other suitable pigments are ci blue pigment 22, 28, C.I · purple pigment 14, 19, 23, 29, 32, ^, 177, and C.I. orange 73. The colorant of the black matrix photopolymerizable composition preferably contains at least one yuan selected from the group consisting of carbon, phoenix black, and iron oxide. However, mixtures of other colorants which give a black appearance as a whole can also be used. For example, the c j f colorants 1 and 7 may be used alone or in combination. 66 (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 593357 A7 ----- E_ V. Description of the invention (64) For any color, A combination of more than two colorants can also be used. Particularly suitable for color filter applications is a powdery processed colorant obtained by dispersing the above colorant in a resin. The colorant concentration in the total solids (colorants and resins of various colors) is, for example, in the range of 5% to 80% by weight, particularly in the range of 20% to 45% by weight. The coloring material of the color filter composition preferably has an average particle diameter smaller than a visible light wavelength (400 nm to 700 nm). Particularly preferred is an average colorant diameter of &lt; 100 nm. If necessary, the colorant can be stabilized in the photosensitive composition by pretreating the colorant with a dispersant to improve the dispersion stability of the colorant in the liquid composition. Preferably, the color filter composition according to the present invention further contains at least one addition polymerizable monomer compound as the component (a). For example, the following compounds can be used alone or in combination with other monomers as addition polymerizable monomers having an ethylenically unsaturated double bond for use in the present invention. In particular, it contains a third butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-acrylpropyl (fluorenyl) acrylate, triethylene glycol di (methyl) ) Acrylate, Trimethylolpropane tri (meth) acrylate, Ethyl-2 • butylpropanediol di (meth) acrylate, Pentaerythritol tri (fluorenyl) acrylate, Pentaerythritol tetra (meth) acrylic acid Esters, dipentaerythritol hexa (fluorenyl) propionate, dipentaerythritol penta (meth) acrylate, polyoxyethylated trimethylol propane di (meth) acrylate, di (2- (methyl) Acrylic fluorenyloxyethyl) isocyanurate, 1,4-diisopropenyl-benzene, 1,4-dihydroxybenzene (meth) acrylate, decyl diol di (meth) acrylic acid Ester, styrene, diallyl -______ This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ~ 67- &quot;-

•,? Τ— (Please read the notes on the back before filling this page) 593357 A7 B7 V. Description of the invention (65 (Please read the notes on the back before filling this page) Fumarate, Triallyl Triphenyl Hexaformate, lauryl (meth) acrylic acid, (fluorenyl) acrylamide and xylene bis (meth) acrylamide. Furthermore, compounds with a hydroxyl group (such as 2-hydroxyl Ethyl (meth) propionic acid, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) propionic acid) and diisocyanates (such as hexamethylidene diisocyanate, The reaction products of toluene diisocyanate and xylene diisocyanate). Particularly preferred are pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and tris (2-propenyloxyethyl) -isocyanate. Urea. In the color resist composition, the total amount of monomers contained in the photopolymerizable composition is preferably 5 to 80% by weight, especially 10 to 70% by weight. Based on the total solids content of the composition (ie, the amount of all components without solvents) Is the benchmark.

As an adhesive for a color filter composition, it is soluble in an aqueous alkali solution and insoluble in water, for example, it may have one or more acid groups and one or more polymerizable unsaturated bonds in the molecule. Homopolymers of polymerized compounds, or one or more copolymers thereof 'and one or more copolymers of polymerizable compounds having one or more unsaturated bonds copolymerizable with this compound may be use. This compound can be obtained by making one or more low molecular weight compounds having one or more acid groups and one or more polymerizable unsaturated bonds in the molecule and one or more having one or more It can be obtained by copolymerizing an unsaturated bond and an acid group-free polymerizable compound copolymerized with these compounds. Examples of the acid group are -COOH group, -S03H group, -S02NHC0- group, novolac group, -S02NH- group and -CO-NH-CO- group. Among them, the South molecular compound having a -COOH group is particularly preferable.

593357 A7 ____ B7_ V. Description of the Invention (66) Preferably, the organic polymer adhesive in the color filter composition contains an alkali-soluble copolymer, which contains at least one unsaturated polymerizable polymerizable monomer unit. Organic acid compounds such as acrylic acid, methacrylic acid, and the like. It is preferable to use unsaturated organic acid ester compounds such as fluorenyl acrylate, ethyl (fluorenyl) acrylate, benzyl (meth) acrylate, styrene as a further co-monomer of the polymer adhesive. Etc. to balance properties such as alkali solubility, adhesive rigidity, chemical resistance, etc. The organic polymer adhesive may be a random copolymer or a block copolymer, for example, as described in US 5368976. Examples of polymerizable compounds having one or more acid groups and one or more polymerizable unsaturated bonds in the molecule include the following compounds: acrylic acid, methacrylic acid, itaconic acid, succinic acid, maleic acid, Vinylbenzoic acid and cinnamic acid are examples of polymerizable compounds having one or more -COOH groups and one or more polymerizable unsaturated bonds in the molecule. Examples of vinylbenzenesulfonic acid and 2- (meth) acrylamido-2-methylpropanesulfonic acid polymerizable compounds having one or more -S03H groups and one or more polymerizable unsaturated bonds . N-methylsulfonyl (meth) acrylamide, N-ethylsulfonyl (meth) acrylamide, N-phenylsulfonyl (meth) acrylamide, and N- (p- An example of a fluorenylphenylsulfonyl) (fluorenyl) acrylamide is a polymerizable compound having one or more -S02NHC0- groups and one or more polymerizable unsaturated bonds. Examples of polymerizable compounds having one or more carboxyl groups and one or more polymerizable unsaturated bonds in the molecule include hydroxyphenyl (fluorenyl) acrylamide, dihydroxyphenyl (fluorenyl) acrylamine, Hydroxyphenyl-carbonyloxyethyl (fluorenyl) acrylate, hydroxyphenyloxyethyl (fluorenyl) acrylate, hydroxybenzene Paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 69 (Please (Please read the notes on the back before filling this page). 、 可 | 593357 A7 B7 V. Description of the invention (67) thiothioethyl (fluorenyl) acrylate, dihydroxyphenylcarbonyloxyethyl (fluorenyl) acrylic acid Esters, dihydroxyphenyloxyethyl (meth) acrylates, and dihydroxy-phenylthioethyl (fluorenyl) acrylates. Examples of polymerizable compounds having one or more -S02NH- groups and one or more polymerizable unsaturated bonds in the molecule include compounds represented by the chemical formula (a) or (b). CH2 = CHA1-Y1- A2-S02-NH-A3 (a) CH2 = CHA4-Y2-A5-NH-S02-A6 (b) where Y! And Y2 each represent -COO-, _CONA7 • or a single bond; Ai and eight 4 mother One represents 表 or CH3; each of A2 and A5 represents a q-Cu alkylene, cycloalkylene, alkylene, or alkylene, or C2-C12 alkylene which optionally has a substituent. In which, ether and thioether groups, cycloalkyl, arylene, or aralkyl are inserted; each of A3 and A6 represents Η, optionally a q-Cu alkyl group having a substituent, a ring Alkyl, aryl, aralkyl; and A7 represents fluorene, optionally substituted crC12 alkyl, cycloalkyl, aryl, or arylalkyl. Polymerizable compounds having one or more -CO-NH-CO- groups and one or more polymerizable unsaturated bonds include maleimide and N-propenyl-propenylamine. These polymerizable compounds become polymer compounds containing -CO-NH-CO- groups in which a ring and a main chain system are formed together by a polymerization reaction. Furthermore, methacrylic acid derivatives and acrylic acid derivatives each having a -CO-NH-CO- group can also be used. These methacrylic acid derivatives and acrylic acid derivatives include, for example, methacrylamide derivatives such as N-ethylmethylmethacrylamide, N-propylmethylmethacrylamine, N-butyl纸张 This paper size applies to China National Standard (CNS) A4 (210X297 mm) 70 (Please read the legal notices on the back before filling in this page)

-、 Tr— ---— 87_____ 593357 A7 V. Description of the invention (68) methacrylamide, N-pentylmethylmethacrylamine, decdecylmethylacrylamide, N-dodecyl Alkyl fluorenyl acrylamide, N-phenyl fluorenyl methacrylamide, N- (p-methylbenzyl) methacrylamide, N_ (p-chlorobenzyl) methyl Methacrylamide, N_ (naphthyl_carbonyl) methacrylamide, N- (phenylethylfluorenyl) -methacrylamide and 'methacrylmethylaminoimine' and have Acrylamide derivatives of these same substituents. These polymerizable compounds are polymerized into compounds having -C0-NH-C0- groups in the side chain. Examples of the polymerizable compound having one or more polymerizable unsaturated bonds and not containing an acid group include compounds having a polymerizable unsaturated bond selected from (meth) acrylates, (fluorenyl) acrylamide, propylene Compounds, vinyl ethers, vinyl esters, and butyrates, and in particular include (meth) acrylates, such as alkyl (meth) acrylates or substituted alkyl (meth) acrylates ( For example, meth (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (fluorenyl) acrylate, butyl (meth) acrylate, pentyl (Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, third octyl (meth) ) Acrylate, chloro-ethyl (meth) acrylate, allyl (meth) acrylate, 2 · hydroxy-ethyl (fluorenyl) acrylate, 2-hydroxypropyl (fluorenyl) acrylate, 4-hydroxybutyl (meth) acrylate, 2,2-di Fluorenyl-3-hydroxy-propyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, Benzyl (fluorenyl) acrylate, methoxy-benzyl (meth) acrylate, chlorobenzyl (fluorenyl) acrylate, this paper size applies to China National Standard (CNS) A4 specifications (210X297) (%) (Please read the notes on the back before filling this page).? Τ 71 71 593357 A7 — __ B7_ V. Description of the invention (69) oleyl (meth) acrylate, tetrahydrofuryl (fluorenyl) acrylate, Amyloxyethyl (fluorenyl) acrylate and aryl (fluorenyl) acrylate (eg, phenyl (meth) acrylate, fluorenyl (meth) acrylate and naphthyl (fluorenyl) acrylate ); (Meth) acrylamide, such as (meth) acryl-amidine, N-alkyl (fluorenyl) propanamine (this alkyl group contains, for example, methyl, ethyl, propyl , Butyl, second butyl, heptyl, octyl, ethylhexyl, cyclohexyl, triethyl and (Methyl), N-aryl (meth) propylamine (this aryl group includes, for example, phenyl, tolyl, nitrophenyl, naphthyl, and hydroxyphenyl), n, N-dialkyl (Meth) acrylamide (this alkyl group includes, for example, methyl, ethyl, butyl, isobutyl, ethylhexyl, and cyclohexyl), N, N-diaryl (fluorenyl) acrylamide (This aryl group includes, for example, phenyl), N-methyl-N-phenyl (fluorenyl) acrylamide, N-hydroxyethyl-N-fluorenyl (meth) acrylamide, N-2 -Ethylamidinoethylethylethyl (meth) acrylamide, N- (phenylsulfonyl) (meth) acrylamide and N_ (p-methylphenyl_sulfonyl) ( Methacrylamide, and N- (p-methylphenyl-sulfonyl) (meth) acrylamide; allyl compounds, such as allyl esters (eg, allyl acetate , Allylhexanoate, allyl caprylate, allyl laurate, capryl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate Esters and allyl lactates), and allyloxyethanol; ethylene ethers, such as Alkylene ether (this alkyl group contains, for example, hexyl, octyl, decyl, ethylhexyl, methoxyethyl, ethoxyethyl, ethyl, 1-methyl-2, 2-Dimethylaminopropyl, 2-ethylbutyl, hydroxyethyl, hydroxyethoxyethyl, dimethylaminoethyl, diethylaminoethyl, butylaminoethyl, benzene Methyl and tetrahydrofuryl), and vinyl aryl ether (this paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 72 (Please read the precautions on the back before filling this page)

593357 A7 £ 7_ V. Description of the invention (70) Aryl includes, for example, phenyl, fluorenyl, chlorophenyl, 2,4-digas-phenyl, naphthyl, and anthracenyl; (Please read first Note on the back, please fill in this page again) Ethyl vinegar, such as ethylene butyrate, vinyl isobutyrate, ethylene trimethyl acetate, vinyl diethyl-acetate, Vinyl borate, vinyl hexanoate, vinyl gas-acetate, vinyl dichloroacetate, vinylmethoxyacetate, vinylbutoxyacetate, vinylphenyl Acetate, vinyl acetoacetate, vinyl lactate, vinyl-b-phenyl butyrate, vinyl gas hexyl carboxylate, vinyl benzoate, vinyl salicylate , Vinyl chlorobenzoate, vinyl tetrabenzate, and vinyl naphthalate. Stilbene, such as stilbene, stilbene (eg, stilbene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropyl Styrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoro-methylstyrene, ethoxymethylstyrene, And ethoxymethylstyrene), alkoxystyrene (for example, methoxystyrene, 4-methoxyfluorenylstyrene, and dimethoxystyrene), and dentylstyrene ( For example, aerostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentafluorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2- Bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene); butenoates, such as alkyl butenoates (eg, butyl butenoates, hexyl) Butenoates, and glycol monobutenoates); Di-based itaconate (such as' dimethyl itaconic acid vinegar, diethyl itaconic acid) This paper is suitable for this paper National standard (° ^) A4 specification (210x297 public love) 73 593357 A7 _B7_ V. Description of the invention (71) Ester, and dibutyl itaconic acid ester); Dialkyl maleate or fumarate (for example , Difluorenyl maleate and dibutyl fumarate); and (meth) acrylonitrile. Homo- or co-polymers of hydroxystyrene, or novolac-type phenol resins, such as poly (hydroxystyrene) and poly (hydroxystyrene-co-vinylcyclohexanol), novolac resin, Cresol novolac resin, and halogenated phenol novolac resin. More specifically, it includes, for example, a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic anhydride copolymer, for example, styrene as a comonomer, and maleic Acid copolymers, and partially esterified maleic acid copolymers, each of which is described in, for example, JP 59-44615-B4 ("JP-B4" as used herein refers to the Japan under review Patent Bulletin), JP 54-34327-B4, JP-58-12577-B4, and JP 54-25957-B4, JP 59-53836-A, JP 59-71048-A, JP 60-159743-A, JP 60-258539-A, JP 1-152449-A, JP 2_ 199403-A, and JP 2-199404-A, and the copolymer can be further reacted with an amine, for example, as disclosed in US 5650263, further on the side chain A cellulose derivative having a carboxyl group can be used, and particularly preferably a copolymer of benzyl (fluorenyl) acrylate and (fluorenyl) acrylic acid and benzyl (meth) acrylic acid vinegar, (meth) acrylic acid, and Copolymers of other monomers, for example, as described in US 4139391, JP 59-44615-B4, JP 60-159743-A, and JP 60-258539-A. Regarding those having carboxylic acid groups in the above-mentioned organic adhesive polymer, it can make some or all of the carboxylic acid groups and glycidyl (meth) acrylates or the paper size applicable to China National Standard (CNS) A4 specifications (210X297 mm) (Please read the notes on the back before filling this page)

74 593357 A7 _B7_ V. Description of the invention (72) Epoxy (meth) acrylate reaction to obtain photosensitivity, coating film strength, coating solvent and chemical resistance, and adhesion to substrate Photopolymerizable organic adhesive polymer. Examples are disclosed in JP 50-34443-B4 and JP 50-34444-B4, US 5153095, T. Kudo et al. J. Appl. Phys., Volume 37 (1998), pages 3594-3603, US 5677385 and The weight average molecular weight of the US 5650233 0 adhesive is preferably 500 to 1,000,000, for example, 3,000 to 1,000,000, and more preferably 5,000 to 400,000. These compounds may be used alone or as a mixture of two or more. The content of the adhesive in the photosensitive resin composition is preferably 10 to 95% by weight, more preferably 15 to 90% by weight, and it is based on all solid materials. Furthermore, in the color filter, the total solid component of each color may contain an ionic impurity scavenger, such as an organic compound having an epoxy group. The concentration of the ionic impurity scavenger in the total solid component is generally in the range of 0.1% to 10% by weight. Examples of color filters, particularly the combination of the aforementioned colorants and ionic impurity scavengers, are shown in EP 320264. It is to be understood that the photoinitiator according to the present invention in the color filter composition described in EP 320264, that is, the compounds of Chemical Formulas I, II, and III may replace the triazine initiator compound. The composition according to the present invention may further include a cross-linking agent activated by an acid (for example, described in JP 10 221843-A) and a compound which generates an acid by heat or by actinic radiation and activates a cross-linking effect. The composition according to the present invention may also contain a latent colorant, which is converted into an excellently dispersed colorant during the heat treatment of the latent colorant containing the photosensitive pattern or coating. The heat treatment can be applied after exposure or latent paper size to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page). Order-75 593357 A7 _____B7_ V. Description of the invention ( 73) The colorant can be applied after the image-forming layer is developed. This latent colorant is a soluble colorant precursor which can be converted into an insoluble colorant by, for example, a chemical, thermal, photolytic or radiation-induced method as described in US 5879855. The conversion of the latent colorant can be promoted by adding a compound that generates an acid during actinic exposure or by adding an acidic compound to the composition. Therefore, a color filter can also be prepared, which is a latent colorant contained in the composition according to the present invention. Examples of color filter inhibitors, their composition and processing conditions are shown in T. Kudo et al. Jpn. J. Appl. Phys. Volume 37 (1998) 3594T. Kudo et al. J. Photopolym. Sci. Technol. Volume 9 (1996) 109; K. Kobayashi's Solid State Technol. 1992, pages S15-S18; US 5368976; US 5800952; US 5882843; US 5879855; US 5866298; US 5863678; JP 06-230212 -A; EP 320264; JP 09-269410-A; JP 10-221843-A; JP 01-090516-A; JP 10-171119-A; US 5821016; US 5847015; US 5882843; US 5719008; EP 881541 or EP 902327. The photoinitiator of the present invention can be used in a color-blocking agent, for example, as exemplified above, or a known photoinitiator that can be partially or completely replaced in the resist. Those skilled in the art can understand that the use of the novel photoinitiator of the present invention is not limited to the special adhesive resins, cross-linking agents and compositions of the color filter examples described above, but can also be combined with dyes or colorants or latent colors. Any polymerizable composition is used to form a photosensitive color filter ink or a color filter. Therefore, the subject of the present invention is also a color filter made by providing red, green, and blue elements and a selective black matrix, all of which include a photosensitive resin and a colorant on a transparent substrate, and On the surface of the substrate or the size of the filter paper, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable (please read the precautions on the back before filling this page) 7 76-593357 A7 I —------- —_ B7 —__ 5. Description of the invention (74) A transparent electrode is provided on the surface of the color layer, wherein the photosensitive resin contains the polyfunctional acrylate monomer as described above, an organic polymer adhesive and chemical formula I, II or ΠΙ. Photopolymerization initiator. The monomer and adhesive components and suitable pigments are as described above. In the preparation of a color filter, a transparent electrode layer may be coated on the surface of a transparent substrate, or may be provided on the surface of red, green, and blue pixels and a black matrix. The transparent substrate is, for example, a glass substrate, which may additionally have an electrode layer on its surface. A black matrix is preferably applied between the color areas of different colors to provide a color filter contrast. In addition to using a photosensitive composition to form a black matrix and patterning the black photosensitive composition by patterning exposure (ie, through appropriate masking) to form a black pattern that separates red, green, and blue areas on a transparent substrate In addition, it can additionally use an inorganic black matrix. This inorganic black matrix can be patterned by appropriate imaging methods (for example, using photolithography with a residual resist to etch an inorganic layer in an area not protected by the resist, and then remove the remaining resist. ) Formed by depositing (ie, spraying) a metal (ie, chromium) film on a transparent substrate. Several different methods are known how and how to apply this black matrix at one step in the color filter preparation method. It can be applied directly on a transparent substrate before forming the red, green and blue (RGB) color filters as described above, or it can also be applied after the RGB color filters are formed on the substrate. In different specific examples of color filters for liquid crystal displays, according to us 5626796, a black matrix can also be coated on a substrate opposite to a substrate carrying RGB color filter elements, which are separated by a liquid crystal layer. If the transparent electrode layer is coated with RGB color filter elements and selective black, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm): 77-I-(Please read the precautions on the back before filling this page ). Equipment, one-T—: line 丨 593357 A7 __ B7 V. Description of the invention (75) After the substrate is deposited, an additional protective film as a protective layer can be applied to the color filter layer before the electrode layer is deposited, for example No. 5,650,263. To form a protective layer for a color filter, a photosensitive resin or a thermosetting resin composition is used. The photosensitive composition of the present invention can also be used to form the protective layer, because the cured film of the composition has flatness, hardness, chemical resistance and heat resistance, transparency (especially in the visible light region), and the substrate. The adhesiveness and the suitability for forming a transparent transparent film (for example, an IT0 film) thereon are excellent. In the preparation of the protective layer, non-essential parts of the protective layer (for example, marking lines for cutting the substrate and the bonding pad of the stereo image sensor) must be removed from the substrate, such as JP57-42009-A, JP1 -130103-A and JP1-134306-A. In this connection, it is difficult to selectively form a protective layer with excellent accuracy using the above-mentioned thermosetting resin. However, the photosensitive composition can easily remove unnecessary portions of the protective layer by photolithography. It is obvious to those skilled in the art that the photosensitive composition of the present invention can be used to generate red, green, and blue pixels and a black matrix for preparing a color filter, regardless of the above-mentioned processing differences. , Can be coated with additional layers and; take into account differences in color device design. The use of the composition according to the present invention to form a color element should not be limited by different designs and the methods of preparing these color filters. The photosensitive composition of the present invention can be used to form a color filter, but is not limited to this application. It can also be used in recording materials, resist materials, protective layers, dielectric layers, display applications and display elements, coatings and printing inks. The photosensitive composition according to the present invention is also suitable for preparing a liquid crystal display (more specifically, a reflective liquid crystal display, which includes a paper sheet having a switching element that is a Chinese standard (CNS) A4 specification (210X297 mm) 78 (please (Read the notes on the back and fill in this page) ★-593357

DISCLOSURE OF THE INVENTION An interlayer insulating layer or a dielectric layer of a thin film transistor (TFT) active matrix type display and a non-switching element passive matrix type). (Please read the precautions on the back before filling out this page.) • tr—line 丨 In recent years, liquid crystal displays have been widely used, for example, pocket TVs and communication terminal devices due to their small thickness and light weight. Reflective liquid crystal displays that do not require the use of back light are particularly needed because they are extremely thin and lightweight, and they can significantly reduce power consumption. However, even if the back light is from a transmissive color liquid crystal display used today and a light reflecting plate is added below the display, it will cause problems due to the low efficiency of using light, and it may not have practical brightness. As a solution to this problem, various reflective liquid crystal displays have been proposed to promote the efficiency of using light. For example, a reflective liquid crystal display is designed to include reflective pixel electrodes. The reflective liquid crystal display includes an insulating substrate and an opposite substrate spaced from the insulating substrate. The space between the substrates is filled with liquid crystal. The gate electrode is formed on the insulating substrate, and the intermediate electrode and the insulating substrate are covered with a gate insulating film. Then, a semiconductor layer is formed on the gate insulating film on the gate electrode. The source electrode and the drain electrode are also formed on the gate insulating film which is in contact with the semiconductor layer. The source electrode, the drain electrode, the semiconductor layer, and the gate electrode cooperate with each other to form a bottom-gate type TFT as a switching element. An interlayer insulating film is formed to cover the source electrode, the drain electrode, the semiconductor layer, and the gate insulating film. Contact holes are formed in the interlayer insulating film on the drain electrode. Pixel electrodes made of aluminum are formed on the interlayer insulating film and on the inner side walls of the contact holes. The drain electrode of the TFT is finally in contact with the pixel electrode via an interlayer insulating film. The interlayer insulating film is generally designed to have a roughened surface, whereby the pixel electrode can be used as a reflecting plate, which diffuses light to obtain a wider viewing angle (visible angle). The pixel electrode is used as a light reflecting plate. The reflective paper size is in accordance with Chinese National Standard (CNS) A4 specification (210x297 public love) 593357 A7 B7 5. Invention description (77) (Please read the precautions on the back before filling in this Page) LCD monitors significantly promote the efficiency of using light. In the above-mentioned reflective liquid crystal display, the interlayer insulating film is designed to have convex portions and concave portions by photolithography. In order to form and control the micrometer-scale fine-shaped protrusions and recesses with a rough surface and to form contact holes, a photolithography method using positive and negative photoresists is used. For these resists, the composition according to the present invention is particularly suitable. ..., order, the photosensitive composition according to the present invention can be further used for preparing a separator ', which controls the element gap of the liquid crystal portion in the liquid crystal display panel. Because the nature of the light transmitted or reflected through the liquid crystal layer in the liquid crystal display depends on the element gap, the thickness accuracy and uniformity on the pixel array are important parameters for the performance of the liquid crystal display unit. In a liquid crystal device, the space between the substrates in the device is maintained fixed by sparsely distributing glass or polymer spheres with a diameter of a few micrometers as a spacer between the substrates. The separator is thus held between the substrates so that the distance between the substrates is maintained at a fixed value. This distance is determined by the diameter of the divider. These spacers ensure a minimum separation between the substrates, that is, they avoid a reduction in the distance between the substrates. However, it cannot be avoided that the substrates are separated from each other, that is, the distance between the substrates is increased. In addition, this method of using separation balls has the uniformity of the diameter of the separation balls, the difficulty of uneven dispersion of the separation balls on the panel, the uneven orientation, and the brightness and / or optical aperture (which depends on the position of the spacers on the pixel array area). Depending on) reduction and other issues. LCD monitors with large image display areas have recently attracted greater attention. However, an increase in the area of a liquid crystal cell generally results in deformation of a substrate constituting the cell. The layer structure of the liquid crystal is easily destroyed by deformation of the substrate. Therefore, even if the separator is used to keep the interval between the substrates fixed. LCD with large image display area 593357

(Please read the precautions on the back before filling out this page) ， 可 | The display is difficult to implement due to interference from the display. Instead of using the above-mentioned separation ball dispersion method, a method of forming a pipe string as a separator in the element gap is proposed. In this method, a resin column is formed as a spacer in a region between a pixel array region and a counter electrode to form a designated element gap. Photosensitive materials with the adhesive properties of photolithography are commonly used, for example, in the preparation of color filters. In terms of the free control of the position, number and height of the partitions, this method is more advantageous than the traditional method using spacer balls. In a color liquid crystal display panel, these spacers are formed in a non-image area under a black matrix of a color filter element. Therefore, a separator formed using a photosensitive composition does not reduce brightness and optical aperture. A photosensitive composition for manufacturing a protective layer with a separator for a color filter is disclosed in JP 2000-81701-A, and a dry film type photoresist of the separator material is also disclosed in Jp 11- 174459-A and JP 11-174464-A. As described in these documents, the photosensitive composition, liquid and dry film photoresist include at least an alkali or acidic soluble adhesive polymer, a radical polymerizable monomer, and a radical initiator. In some cases, thermally crosslinkable components such as epoxides and carboxylic acids may be additionally included. The steps for forming the separator using the photosensitive composition are as follows: The photosensitive composition is applied to a substrate (for example, a color filter panel), and after the substrate is pre-baked, it is exposed through a mask. The substrate is then developed with a developer and patterned to form a desired separator. When the composition contains certain thermosetting components, in general, post-baking is performed to thermally cure the composition. The photocurable composition according to the present invention is suitable as a separator for manufacturing a liquid crystal display (as described above) because of its high sensitivity. The photosensitive composition according to the present invention is also suitable for the manufacture of liquid crystal displays. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 81 593357 A7 ___B7_ V. Description of the invention (79) Panel and image sensor Wait for the microscope sheet array. Microscope sheets are pure optical components of microscopes, which are arranged on active optoelectronic devices such as detectors, displays, and light-emitting devices (light-emitting diodes, lateral and vertical cavity lasers) to improve their optical input and output Quality. Application areas are broad and cover areas such as electricity, information technology, audiovisual services, solar cells, detectors, solid-state light sources, and optical interconnects. Today's optical systems use a variety of different techniques to achieve efficient coupling between microscope lenses and micro-optical devices. Microscope sheet arrays are used to focus the irradiated light on the pixel area of a non-luminous display device such as a 'liquid crystal display device' to increase the brightness of the display, to focus incident light, or as a line for, for example, a fax machine, Image sensing 1§ The device for forming an image on the photoelectric conversion area to improve the sensitivity of these devices' and to form a blanket on a photosensitive device for a liquid crystal printer or a light emitting diode (LED) printer Printed image. The most common application is to improve the efficiency of photodetector arrays of solid-state image sensing devices such as charge coupled devices (CCDs). In a detector array, the collection of as much light as possible for each detector element or pixel is required. If a microscope sheet is placed on top of each pixel, the lens collects incident light and focuses it on an active area smaller than the size of the lens. According to conventional techniques, the microscope sheet array can be manufactured by various methods. (1) A method for obtaining a convex lens sheet, in which the lens pattern of a planar structure is etched on a thermoplastic resin by conventional photolithography techniques, and then thermoplastic The resin is heated to a temperature above the softening point of the resin to make it fluid, thereby causing indentation at the end of the pattern (so-called, flowing back,,) (see, for example,

JP 60-38989-A, JP 60-165623-A, JP 01-67003-A, and JP 82 (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) 593357 A7 B7 V. Description of the invention (80) 2000-39503-A). In this method, the thermoplastic resin used is photosensitive and the lens pattern can be obtained by exposing this resin. (2) A method of forming a plastic or glass material by using a mold or a compression mold. As lens materials, photocurable resins and thermosetting resins can be used in this method (see, for example, WO99 / 38035). (3) A method of forming a convex lens based on the following phenomenon: When a photosensitive resin is exposed in a desired pattern by using a calibrator, unreacted monomers move from the unexposed area to the exposed area, causing the exposed area to expand (see, For example, the Journal of the Microscopy Research Group of the Applied Physics Society, Optics Seminar, Volume 5, No. 2, pp. 118-123 (1987) and Volume 6, No. 2, pp. 87-92 (1988)). On the upper surface of the material, a photosensitive resin layer is formed. Thereafter, by using an individual mask, the upper surface of the photosensitive resin layer is irradiated with light such as a mercury lamp, and the photosensitive resin layer is thus exposed. Therefore, the exposed portion of the photosensitive resin layer is expanded into a convex lens shape to form a light-collecting layer having a plurality of microlenses. (4) A method for obtaining a convex lens, in which a photosensitive resin is exposed by a near-exposure technique, in which a photomask is not in contact with the resin to cause a blur at the edge of the pattern. Thus, the amount of the photochemical reaction product is determined by the blur at the edge of the pattern. Degrees (see, for example, JP 61-153602-A). (5) A method for producing a lens effect, in which a photosensitive resin is exposed to light with a special intensity distribution to form a refractive index distribution pattern depending on the intensity of light (see, for example, JP 60-72927-A and JP 60-166946-A ). The photosensitive composition according to the present invention can be used in any of the above methods to use 83 (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 593357 A7 B7 V. Description of the invention (81) The photocurable resin composition forms a microscope sheet. A special kind of technology focuses on forming a microscope sheet in a thermoplastic resin such as a photoresist. An example is disclosed in SPIE 898 References, Popovic et al., Pp. 23-25 (1988). This technique (called reflow technique) involves steps in a photosensitive resin, such as a photoresist, by, for example, photolithography to define the traces of a lens in a thermoplastic resin, and thereafter heating the material above it Reflux temperature. The surface tension causes the photoresist island to stretch into a spherical cap, which has the same volume as the original island before reflow. This cap is a plano-convex lens. The advantages of this technology are the simplicity, reproducibility, and possibility of direct integration on top of the light-emitting or light-detecting photovoltaic device. In some cases, a protective layer is formed on a patterned lens unit. The lens has a rectangular shape before reflow to avoid blurring of resin islands in the middle, and does not reflow into a spherical cap in the reflow step. This protective layer acts as a permanent protective layer. The coating layer is also made of a photosensitive composition. Microscope arrays can also be made by using, for example, the molds or dies described in EP0932256A2. The method of preparing a flat microscope sheet array is as follows: a mold release agent is coated on the forming surface of the stamper, and convex portions are densely arranged thereon, and a light-curable synthetic resin material having a high refractive index is fixed On the forming surface of the stamper. Second, a basic glass plate is pushed onto a synthetic resin material, thereby spreading the synthetic resin material, and the synthetic resin material is cured by irradiation with ultraviolet radiation or by heating, and is formed to form a convex microscope sheet. Thereafter, the stamper was peeled. Then, a light-curable synthetic resin material having a low refractive index is additionally coated on a convex microscope sheet as an adhesive layer, and a glass substrate made of a cover glass plate is pushed onto the synthetic resin material 84 (please read the back first) Please pay attention to this page and fill in this page again) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 593357 A7 ______B7_ V. Description of the invention (82) It is used to expand it. Then, the synthetic resin material is cured, and a final planar microscope sheet array is formed. As disclosed in US 5969867, a similar method using a mold is applied to the manufacture of a prism sheet, which is used as a part of a back light unit of a color liquid crystal display panel to promote brightness. Three cymbals forming two rows on one side are placed on the light-emitting surface of the back light. In order to prepare a three-lens tablet, the active energy ray-curable composition is cast and unfolded in a lens mold (which is made of metal, glass, or resin), and formed into a lens shape such as a three-lens row. Thereafter, it is transparent A substrate sheet is placed thereon, and an active energy ray from an active energy ray emitting source is irradiated through the sheet to be cured. Then, the obtained lens sheet was released from the lens mold to obtain a lens sheet. The active energy ray-curable composition used to form the lens segment needs to have various properties, including adhesion to a transparent substrate, and appropriate optical characteristics. Mirrors with at least certain photoresist techniques are undesired for some applications because the blue end of the optical spectrum has poor optical transmission. Since the photo-curable composition according to the present invention has low changeable properties (under heating and photochemistry), it is suitable for preparing the microscope sheet array as described above. The novel radiation-sensitive composition is also suitable for use in photolithography steps of plasma display panel (PDP) preparation methods, especially image formation methods for barrier ribs, phosphor layers, and electrodes. The PDP is a flat display that emits light and emits light to display images and information. By the panel construction and operation method, two types are known, namely, a Dc (direct current) type and an AC (alternating current) type. For example, the principle of the color pDp of the DC type is briefly explained. For DC-type color PDP, between two transparent substrates (one paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) 85 (Please read the precautions on the back before filling this page)

593357 A7 ____B7_ V. Description of the invention (83) General glass plate) The space between grids is divided into several small units by grid-like barrier ribs placed between transparent substrates. In individual units, the exhaust gas (such as He or Xe) is sealed. A phosphor layer is formed on the rear wall of each unit, which emits visible light of three main colors when excited by ultraviolet rays generated by exhaust gas emission. On the inner surface of the two substrates, the electrode systems are placed opposite each other across the relevant unit. Generally, the cathode is formed of a film of a transparent conductive material such as NESA glass. When voltage is applied between these electrodes formed on the front and rear walls, the discharge gas sealed in these units induces plasma discharge, and causes ultraviolet, red, blue and green fluorescent elements to emit light. And make the display produce an image. In a full-color display system, the individual three fluorescent elements of the three main colors of red, blue, and green described above are combined to form a pixel. The cells in the DC-type PDP are divided by the barrier ribs of the component of the crystal lattice, and in the AC-type PDP are divided by the barrier ribs arranged parallel to each other on the substrate surface. In either case, these units are divided by barrier ribs. These barrier ribs are used to confine light emission to a fixed area to eliminate erroneous emissions or crosstalk between adjacent emission units and ensure ideal display. The composition according to the present invention has also been found to be applied to the manufacture of one or more layers of single- or multi-color image recording or image reproduction (photocopying, reproduction). Furthermore, this material is suitable for a color verification system. In this technique, a composition containing microcapsules can be applied, and for image manufacturing, heat treatment can be applied after radiation curing. Such systems and technologies and their applications are disclosed, for example, in US 5376459. Light curing is very important for print systems, because the drying time of the ink is an important factor in the production rate of the image product, and it needs to be instant grade. The size of the purple paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public copy) 86 (Please read the precautions on the back before filling in this page)-Order ·… line 丨 593357 A7 __-____ B7_ V. Description of the invention (84) Outside-curable inks are especially important for screen and offset printing systems. As already mentioned above, this novel mixture is also highly suitable for preparing printing plates. This application uses, for example, soluble linear polyamides or styrene / butadiene and / or styrene / isoprene rubber, polyacrylates or carboxyl-containing polymethylmethacrylates, polyvinyl alcohol or A mixture of an amino acrylate and a photopolymerizable monomer, such as acrylamide and / or methacrylamide, or an acrylate and / or methacrylate, and a photoinitiator. The films and plates (wet or dry) of these systems are exposed to the negative (or positive) of the original being printed, and the uncured parts are subsequently washed off with a suitable solvent or aqueous solution. Another area where photocuring is used is metal coatings, such as coatings on metal plates and pipe fittings, cans or bottle caps, and photocuring of polymer coatings, such as PVC-based flooring or Wall covering. Examples of light curing of paper coatings are colorless painting of labels, record covers and book covers. Also of interest are shaped articles made from the composite composition using this novel photoinitiator. This compound is composed of a self-supporting matrix material (for example, glass fiber fabric, or another type of plant fiber) [cf. K.-P. Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370]. This photocurable composition was impregnated. When prepared using this novel compound, molded parts containing composite compounds achieve a high degree of mechanical stability and resistance. This novel compound can also be used, for example, as a photocuring agent in molding, impregnating and coating compositions as described in EP 7086. Examples of this composition are gel-coated resins (which accept stringent requirements regarding curing activity and yellowing resistance), and fiber-reinforced moldings (e.g., light-diffusion panels, which are flat or have long papers) Dimensions are applicable to China National Standard (CNS) A4 (210 X 297 mm) 87 (Please read the precautions on the back before filling this page)

593357 A7 _B7_ V. Description of the invention (85) (Please read the precautions on the back before filling this page) or cross wrinkles. Techniques for preparing such moldings (such as hand layup, spray layup, centrifugal casting, or filament winding) are described, for example, in `` Glasfaserverstarkte Kunststoffe '' by PH Selden, page 610, Springer Verlag Berlin -Heidelberg-New York 1967 〇 Examples of objects that can be made by such technologies are ships, fiberboard or cardboard with double-sided glass-reinforced plastic coatings, pipes, containers, etc. Molding, impregnation, and coating Further examples of the composition are UP resin gel coatings containing glass fiber (GRP) moldings such as wrinkled sheets and paper laminates. The paper laminates may be urea resin or melamine resin. Mainly. Before manufacturing this laminate, a gel coat is made on a support (for example, a film). This novel photocurable composition can also be used for casting resins or embedded objects, for example, Electronic components, etc. The compositions and compounds according to the present invention can be used to prepare holograms, wave guides, and optical switches, where development is performed by using the difference in refractive index between the illuminated and unirradiated areas. Photocuring compositions are also important in the development of optical technology and in the optical preparation of information carriers. For these applications, as described above, the layer (wet or dry) applied to the support is, for example, UV or Visible light is imagewise irradiated, and the unexposed areas of this layer are removed by treatment with a developer. The application of a photo-curable layer to a metal can also be accomplished by electrodeposition. The exposed areas are polymerized by crosslinking, And therefore it is insoluble and remains on the support. Appropriate coloring produces a visible image. If the metallization layer of the support system, this metal can etch away unexposed areas after exposure and development or by plating strength. In this way can be Generate electronic circuits and photoresist. When used as the material for forming the image, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm) 593357 A7 B7 V. Description of the invention (86 (Please read the precautions on the back before (Fill in this page) It is expected that the novel photoinitiator provides excellent performance in producing so-called printed images, whereby color changes are induced by irradiation. To form this printed image, different dyes and / Its white form is used, and examples of such print-out imaging systems can be found in, for example, WO 96/41240, EP 706Q91, Ep 511403 EP 511403, US 3579339 and US 4622286. This novel photoinitiator is also suitable A composition for forming a light formable pattern of a dielectric layer of a multilayer multilayer circuit board manufactured by a sequential build-up method. As described above, the present invention provides a method for manufacturing colored and non-colored substrates. Colored paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coatings, photoresists for electronic products, such as plating resists, etching resists, liquids and Dry film, solder resist, used to prepare color filters for various display applications or to produce plasma display panels (eg, barrier ribs, phosphor layers, electrodes), electroluminescent displays, and LCDs (eg, interlayer insulation Layer, separator, microscope sheet array) in the preparation method of the structure of the composition of the resist, as a component of the package of electrical components and electronic components, used to manufacture magnetic recording materials, micromechanical parts, wave guides, Optical switches, electroplated masks: etching masks, color verification systems, glass fiber coatings, screen printing printing stencils, used to prepare three-dimensional objects by stereolithography, and as image recording materials, especially It is a decoloring material used for holographic recording, microelectronic circuits, decoloring materials, image recording materials, and image recording materials using microcapsules. Substrates for photographic materials rfU | § include, for example, polymer films, cellulose acetate or polymer-coated paper; substrates for offset printing

This paper size applies to the Zhongguanjia standard (_ M specification (21GX297 public T 593357) V. Description of the invention (87 Material is specially treated aluminum, and the substrate used to make printed circuits is a copper electroplated laminate. The substrate for manufacturing integrated circuits is, for example, silicon wafers. The layer thickness of photosensitive layers used in photographic materials and offset printing is generally about 0.5 / zm to 10 / zm, and for printed circuits it is.丨 From 茁 to about 100 &quot; m. After the substrate is coated, the solvent is removed, which is generally made by drying to leave the photoresist coating on the substrate. Coating can be completed by applying a liquid composition, solution or suspension to the substrate. The choice of solvent and concentration is mainly based on the type of composition and coating technology. The solvent must be inert, that is, it must not be combined with the group. Parts are chemically reacted and need to be removed again during drying after coating. Examples of suitable solvents are ketones, ethers and esters such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone , N-methylpyrrolidone, dioxane, tetrahydrofuran, 2 · methoxyethanol, 2-ethyl Ethyl alcohol, methoxypropanol, dimethoxyethane, ethyl acetate, n-butyl acetate, ethyl 3-ethoxypropionate, 2-methoxypropyl acetate, methyl methyl Oxypropionate, xenopentanone, 2-pentanone, and ethyl lactate. The solution is uniformly applied to the substrate by known coating techniques, for example, by spin coating, dip coating, doctor blade coating Coating, curtain coating, painting, spraying (especially by electrostatic spraying), and reverse roll coating, or by electrophoretic deposition. This photosensitive layer can also be applied to a temporary flexible support, It is then applied to the final substrate (for example, a copper-plated circuit board or glass substrate) by transferring this layer through lamination. The amount of coating (coating thickness) and the nature of the substrate (layer substrate) It depends on the field of application. The coating thickness range generally includes the value of about 0_1 # m to more than loo # m, for example, 0.1 / zm to lcm, preferably 0.5 // m to 1000 # m. Paper Size Applicable to China National Standard (CNS) A4 specification (210X297 mm) 90 (Please read the precautions on the back before filling this page)

可可 593357 A7 _B7_ V. Description of the invention (88) After the substrate is coated, the solvent is removed (usually by drying) to leave the photoresist film which is basically dry. On the substrate. The photosensitivity of the novel composition generally extends from about 150 nm to 600 nm, for example, 190-600 nm (ultraviolet-visible region). Appropriate radiation is present, for example, in sunlight or light from artificial light sources. Therefore, a large number of very different types of light sources are used. Point light sources and arrays ("light blankets") are suitable. Examples are lamp arc lamps, xenon arc lamps, low-, medium-, high- and ultra-high-pressure mercury lamps, which can have metal halide dopants (metal-halogen lamps), microwave laser metal vapor lamps, lasers Element lamps, ultra-optical fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flashes, photographic giant lamps, light emitting diodes (LEDs), electron beams and X-rays. The distance between the lamp and the substrate being exposed according to the present invention may vary depending on the desired application and the type and output of the lamp, and may be, for example, 2 cm to 150 cm. Laser sources (for example, excimer lasers, such as F2 excimer lasers for 157 nm exposure, KrT excimer lasers for 248 nm exposure, and ArF excimer lasers for 193 nm exposure) are also suitable. Lasers in visible light areas are also used. The term "imaging" exposure includes exposure through a mask containing a predetermined pattern (eg, a slide, a chrome mask, a stencil mask, or a wire mesh), or by laser or beam exposure, such as when applied The substrate surface is removed by computer control and an image is generated in this way. A suitable ultraviolet laser exposure system for this purpose is, for example, provided by WEtecandOrbotech (DP · 100 ™ DIRECT IMAGING SYSTEM). Computer controlled irradiation can also be achieved by electron beams. A mask made of liquid crystal can also be used, which can be digitally addressed by pixel addressing, for example, A. Bertsch, (please read the precautions on the back before filling this page). _ 、 ^ Τ—… Line 丨 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 91 593357 A7 B7 V. Description of invention (89) (Please read the precautions on the back before filling this page) JY Jezequel, JC Andre Yu Guang Journal of Chemistry and Photobiology; Chemistry 1997, 107, pp. 275-281 and K. P. Nicolay, described in Offset Printing 1997, 6, pp. 34-37. After the imagewise exposure of this material and before the development, the heat treatment is advantageously performed for a short time. After development, thermal post-baking can be performed to harden the composition and remove all traces of the solvent. The use temperature is generally 50-250 ° C, preferably 80-220 ° C; the heat treatment time is generally between 0.25 and 60 minutes. The photocurable composition can additionally be used in a method for manufacturing a printing plate or a photoresist, for example, as described in DE 4013358. In this method, the composition is exposed to visible light at a wavelength of at least 400 nm for a short time before, at the same time as, or after the image-type irradiation. After exposure and heat treatment (if implemented), the unexposed areas of the photosensitive coating are removed with a developer in a manner known per se. As already mentioned, this novel composition can be developed with an aqueous alkaline solution or an organic solvent. Particularly suitable aqueous alkaline developer solutions are aqueous solutions of tetraalkylammonium hydroxide or metal salt, salt, hydroxide, and carbonate. Small amounts of wetting agents and / or organic solvents can also be added to these solutions if desired. Examples of typical organic solvents that can be added to the developer liquid in small amounts are cyclohexanone, 2-ethoxyethanol, toluene, acetone, or a mixture of these solvents. Depending on the substrate, a solvent (eg, an organic solvent) can also be used as a developer, or as described above, a mixture of an aqueous alkali and these solvents can also be used. Particularly useful solvents for solvent development include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Mono-n-butyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ester The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 92 593357 A7 _______B7_ V. Description of the invention (90) Ester, ethyl-3-ethoxypropionate, methylmethoxypropionate, n-butyl acetate, benzyl alcohol, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone , 2-heptyl-, 2-pentanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphonium, ethyl lactate, Methyl lactate, ε-caprolactam and N-methylpyrrolidone. Optionally, water can be added to these solvents up to an amount where it still obtains a clear solution and sufficient solubility of the unexposed areas of the photosensitive composition is maintained. Accordingly, the present invention also provides a compound containing an ethylenically unsaturated double bond (ie, a monomer, oligomer, or polymer compound containing at least one ethylenically unsaturated double bond, which includes at least one Photoinitiator of chemical formula I, II or III) and photopolymerization with electromagnetic radiation (especially light with a wavelength of 150 to 600 nm (especially 190-600 nm)), electron beam or X-ray irradiation Composition method. The present invention further provides a coated substrate, which is coated on at least one surface with the composition as described above, and is a method for producing a relief image, wherein the coated substrate receives an image type After exposure, the unexposed portion is removed with a developer. Image-wise exposure can be produced by irradiation through a mask or by laser or electron beam as described above. Particularly advantageous in this context are laser beam exposures as described above. The composition of the invention has good thermal stability and low volatility, and is also suitable for photopolymerization in the presence of air (oxygen). Furthermore, only low yellowing is caused in the composition after photopolymerization. The following examples illustrate the invention in more detail. Unless otherwise stated, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) '-(Please read the precautions on the back before filling this page)

593357 A7 -— B7_ V. Outline of Invention (91 ^ '&quot; — &quot; ~ — In addition, parts and percentages are by weight as in the rest of the description and in the scope of the patent application. If there are more than 3 When a carbon atom is mentioned and a specific isomer is not indicated, it is meant in each case as an n-isomer. Example 1: H6-benzylidene 9-ethyl, Xin Xiaogang brick 0-B Synthesis of the acid ester in the formula (I), Ar n-C7H15 H6-benzylidene'9-ethyl-9 · Η · -frazol-3_yl) -oct-1-one in 40 liters of CHfl2 7.83 g (40.1 亳 mol) of N-ethylcarbazole, 5.91 g (42.0 亳 mol) of benzamidine gaseous and 5.88 g (44.1 亳 mol) of Alcl3 were added. After stirring for 4 hours at room temperature, 6 89 g (42 3 mmol) of octyl chloride and 5.92 g (44.4 mmol) of A1C13 were added. The reaction mixture was stirred at room temperature for 4 5 hours. The reaction mixture was then poured into ice water. The product was extracted with CH2C12. This CH2C12 layer was washed with water, saturated NaHC03 aqueous solution and brine, and then dried over anhydrous MgS04. Purification on silica gel by column chromatography using cH2Cl2 · hexane (1: 1) as eluent yielded 12.7 g of a white solid (74.2%). The structure was confirmed by ijj-NMR spectrum (CDC13). 6 [ppm]: 0.89 (t, 3H), 1.20-1.57 (m, 11H), 1.79 (t, 2H), 3.09 (t, 2H), 4.45 (q, 2H), 7.54 (m, 3H) , 7.61 (dd, 2H), 7.85 (dd, 2H), 8.09 (d, 1H), 8.19 (d, 1H), 8.64 (d, 1H), 8.74 (d, 1H). This paper size applies to Chinese National Standard (⑽) A4 (210X297 mm) -94-

----- (Please read the notes on the back before filling this page). Order — 593357 V. Description of the invention (92)

Ul 1- (6-benzylidene-9-ethyl-9 · Η · -carbazol-3-yl) _octyl_bugang will be ammonium hydroxyhydride (0.39 g) dissolved in 5 ml of water 5 · 57 mmol) and sodium acetate (0.54 g, 6.57 Emole) 1- (6-benzylidene-9-ethyl-9 · -9 · -carbazole- 3-yl) _octyl_one_one (2 14 g; 5.03 mole). After refluxing for 7 hours, Zeo was added to the reaction mixture, and the white solid formed was filtered off, washed with water and dissolved in tetrahydrofuran (THF). After drying this THF solution over anhydrous MgS04, it was concentrated under reduced pressure to give 2.16 g of a pale yellow solid (97%). The structure was confirmed by 1h_nmr spectrum (CDC13). (5 [ppm]: 0.85 (t, 3H), 1.20-1.70 (m, 13H), 2.90 (tt, 2H), 4.40 (g, 2H), 7.51 (m, 3H), 7.61 (t , 2H), 7.84 (m, 2Η), 8.65 (dd, 1Η), 8.32 (d, 1Η), 8.63 (d, 1Η). This solid was used in the next reaction without further purification. .

Li 1- (6-benzylidene-9-ethyl-9 · Η · -phyllyl-3-yl) -octane-1-methylacetate S-acetate 1- (6-phenylfluorenyl- 9-Ethyl-9.fluorenyl-carbazol-3-yl) -octane-1-_neck (2.09 g; 4.75 mmol) was contained in 25 ml of tert-butyl methyl ether. To this solution, vaporized acetamidine (0.53 g, 4.75 mmol) was added, and then 1 liter of triethylamine was added dropwise at 10 ° C. After stirring at room temperature for 2.5 hours, the reaction mixture was poured into water, and the product was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of NaHC03, then washed with brine, and then dried with sulfuric acid. After concentration, it was purified on a silica gel by column chromatography using CI ^ Cl2-hexane (2: 1) as the eluent, yielding 67 g of slightly brown UO (m, 13H), 2.28 (s , 3H), 2.96 (t, 2H), 4.43 (q, 2H), 7.43-7.65 (m, 5H), 7.84 (dd, 2H), 7.93 (dd, 1H), 8.08 (dd , Zhang Zhijia Standard (⑽M specifications ^^ 97 public love)-7-95 ~:-593357 A7-R7 V. Description of the invention (93) 1H), 8.44 (dd, 1H), 8.62 (s, 1H) . Examples 2-13 The compounds of Examples 2-13 were prepared according to the method described in Example 1 and from the corresponding aldehydes or ketones. The compounds and iH-NMR data are shown in Tables 1 and 2. Table 1 Example ΑΓι Ri r2 State / Melting point [° c]! H-NMR δ rppm] 2 9 ch3 Positive-C7H15 85-86 '~-0.88 (t, 3H), 1.20-1.65 (m, 10H), 2.27 (s, 3H), 2.83 (t, 2H), 7.34 (d, 2H), 7.48 (m, 4H), 7.59 (m, 1H), 7.72 (m, 4H), 7.78 (dd, 2H) 3 20σ ch3 H 141-142 2.22 (s, 3H), 5.19 (s, 2H), 7.01 (d, 2H), 7.26 (d, 2H), 7.41 (d, 1H), 7.41 (d, 2H), 7.53 (d , 4H), 7.69 (d, 4H), 7.79 (d, 2H), 8.30 (s, 1H) 4 9. Paper jac, phenyl n-C7H15 64-66 0.85 (t, 3H), 1.20-1.80 (m , 8H), 2.92 (t, 2H), 7.43 (d, 2H), 7.44-7.56 (m, 6H), 7.61 (td, 1H), 7.65 (td, 1H), 7.81 (m, 4H), 8.12 ( m, 4H) 5 Q. ch3 H 62-70 2.22 (s, 3H), 5.19 (s, 2H), 7.02 (m, 4H), 7.17 (m, 6H), 7.31 (m, 4H), 7.52 (d, 2H), 7.70 (m , 4H), 7.80 (d, 2H), 8.30 (s, 1H) 6 9 Λ) ch3 H 160 2.23 (s, 3H), 5.21 (s, 2H), 7.04 (d, 2H), 7.41 (t, 1H ), 7.45 (t, 2H), 7.56 (d, 2H), 7.66 (d, 2H), 7.71 (m, 4H), 7.87 (d, 2H), 7.90 (d, 2H), 8.31 (s, 1H) (Please read the notes on the back before filling this page)

， 可 I This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 96 593357 A7B7 V. Description of the invention (94) 7 ch3 H 67-69 1.24 (t, 6H), 2.31 (s, 3H), 3.45 (q, 4H), 5.35 (d, 2H), 6.66 (d, 2H), 7.30 -8.00 (m, 13H), 9.04 (d, 1H), 9.22 (s, 1H) 8 0 σ ch3 H 139 2.23 (s, 3H), 5.47 (s, 2H), 7.00 (d, 2H), 7.58-7.72 (m, 4H), 7.88-8.08 (m, 4H), 8.29 (s, 1H), 8.53 (s, 1H ) 9 9 ° W〇, H3C &quot; 0 ch3 H 139-146 2.22 (s, 3H), 2.40 (tt, 2H), 3.92 (s, 3H), 4.29 (m, 4H), 6.91 (, 3H), 7.13 (dd, 1H), 7.39 (d, 1H), 7.48 (m, 3H), 7.60 (td, 1H), 7.86 (dd, 2H), 8.08 (s, 1H), 8.28 (s, 1H) 10 f n-C3H7 ch3 positive-C3H7 104-108 1.01 (t, 6H), 1.60 (qt, 2H), 1.78 (qt, 2H), 2.27 (s, 3H), 2.83 (t, 2H), 2.95 (t, 2H ), 7.32 (d, 2H), 7.40-7.50 (m, 6H), 7.72 (m, 6H), 7.91 (d, 2H) 11 ch3 ch3 H 176-177 2.32 (s, 3H), 3.50 (s, 3H ), 4.14 (s, 3H), 6.87 (d, 1H), 6.98 (d, 2H)? 7.45 (dd, 1H)? 7.51 (t, 1H), 7.80 (m, 4H), 8.03 (dd, 6H) , 8.45 (s, 1H) 12 ^ Kxy1 c2h5 phenyl n-C7H15 48-56 0.86 (t, 3H), 1.22-1.65 (m, 11H), 2.29 (s, 3H), 2.85 (t, 2H), 4.45 (q, 2H), 7.52 (m, 4H), 7.63 (t, 1H), 7.86 (dd, 2H), 8.09 ( dd, 1H), 8.30 (dd, 1H), 8.66 (d, 1H), 8.86 (d, 1H) (Please read the notes on the back before filling out this page)-、 可 |; 梦 _ This paper size is applicable to China National Standard (CNS) A4 Specification (210X297 mm) 97 593357 A7B7 V. Description of Invention (95) 13 9. C2h5 ch3 Positive-c7h15 Liquid 0.86 (t, 3H), 1.22-1.70 (m, 11H), 2.24 (s , 3H), 2.85 (t, 2H), 4.45 (q, 2H), 7.52 (m, 4H), 7.63 (t, 1H), 7.86 (dd, 2H), 8.09 (dd, 1H), 8.30 (dd, 1H), 8.66 (d, 1H)? 8.86 (d, 1H) 14 〇pxxsja ch3 positive-C7H15 liquid 0.87 (t, 3H), 1.24-1.39 (m, 8H), 1.56 (tt, 2H), 2.26 (s , 3H), 2.83 (t, 2), 7.27 (dd, 2H), 7.46-7.58 (m, 6H), 7.72 (dd5 2H), 7.76 (dd, 2H), 7.92 (dd, 2H), 8.00 (dd , 1H)? 8.06 (dd, 1H) 15 0FXXsXX ch3 positive-c7h15 143-145 1.00 (t, 3H), 1.60 (qt, 2H), 2.25 (s, 3H), 2.80 (t, 2H), 7.24 (dd , 2H), 7.34 (dd, 1H), 7.40 (m, 3H), 7.46 (dd, 2H), 7.54 (m, 2H), 7.65-7.75 (m, 6H) 16 ο Φ h 9〇η2 0 ch3 H 118-121 2.23 (s, 3H), 4.41 ( s, 4H), 7.00 (m, 4H), 7.27 (dd, 2H), 7.40 (m, 3H), 7.52 (dd, 2H), 7.66 (dd, 2H), 7.70 (dd, 2H), 7.80 (dd , 2H), 8.31 (d, 1H) 17 jO V〇09Wn2i &lt; ch3 H liquid 2.21 (s, 3H), 5.17 (s, 2H), 5.21 (s, 2H), 6.91 (m, 4H), 7.21 (dd, 2H), 7.37 (m, 3H), 7.50 (m, 6H), 7.72 (m, 6H), 8.32 (s, 1H) 18 ο Φ Vv 9 ch〇-o-ch2 0 ch3 H 97-99 2.06 (s, 3H), 2.32 (tt, 2H), 4.22 (t, 2H), 4.26 (t, 2H), 6.94 (dd, 2H), 7.00 (dd, 4H), 7.22 (dd, 6H), 7.36 (m, 3H), 7.49 (dt, 2H), 7.62 (dd, 2H), 7.76 (dd, 2H), 7.81 (dd, 2H), 9.86 (s, 1H) (Please read the notes on the back before filling This page). Ordering — This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 98 593357 A7 B7 V. Description of the invention (96 19 § Φ 0 ch3 H 102-111 1.68 (tt, 2H), 1.86 (tt, 4H), 2.20 (s? 3H), 4.03 (m? 4H), 6.90 (dd, 4H), 7.24 (d, 2H), 7.37 (m, 3H), 7.48 (dd, 2H), 7.64 ( dd, 4H), 7.76 (dd, 2H), 8.26 (dd, 2H) 20 Ο Λ 0 ch3 H 121-124 2.00 (tt, 4H), 2.21 (s, 3H), 4.09 (d, 4H), 6.86 ( m, 4H), 7.22 (dd, 2H), 7.39 (m, 3H), 7.50 ( dd, 2H), 7.62 (m, 4H), 7.77 (dd, 2H), 8.28 (s, 1H) 21 φ ch3 H 97 2.20 (s, 3H), 5.20 (s, 3H), 7.00 (dd, 2H) , 7.24 (dd, 4H), 7.42-7.90 (m, 26H), 8.32 (s, 1H) 22 Ο Λ, 0 ch3 C2H5 118-121 2.27 (s, 3H), 2.27 (s, 3H), 5.22 (s , 2H), 7.02 (dd, 2H), 7.25 (m, 4H), 7.40 (m, 3H)? 7.52 (dt, 4H), 7.69 (dd, 2H), 7.79 (dd, 2H), 8.12 (dd, 2H) 23 Ο X h_r $ ίί-〇- ^ 0 ch3 ch3 133-138 1.12 (t, 13H), 2.90 (q, 2H), 5.20 (s, 2H), 7.00 (dd, 2H), 7.23 (dd, 2H), 7.40 (m, 3H), 7.52 (dt, 4H), 7.68 (dd, 2H), 7.78 (dd, 2H), 7.96 (dd, 2H) 24 (Q '' L ο '' 2 ch3 phenyl 81- 86 2.20 (s, 3H), 7.15-7.63 (m, 19H), 7.76-7.86 (m, 8H) 25 ρ 0 ^ Cp C2H5 ch3 positive-c3h7 52 1.05 (t, 3H), 1.50 (t, 3H), 1.85 (qt, 2H), 3.10 (t, 2H), 4.40 (q, 2H), 7.46-7.56 (m, 4H), 7.63 (dd, 2H), 7.85 (dd, 2H), 8.10 (dd, 1H) , 8.20 (dd, 1H), 8.64 (d, 1H), 8.74 (d, 1H) (Please read the notes on the back before filling out this page) Order — Static _ This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 593357

7 7 AB V. Description of the invention (97) 26 p Ό ^ ρ c2h5 ch3 ch3 126 1.47 (t, 3H), 2.27 (s, 3H), 2.49 (s, 3H), 4.42 (q, 2H), 7.48 (m , 4H), 7.52 (td, 1H), 7.83 (dd, 2H), 7.98 (dd, 1H), 8.08 (dd, 1H), 8.44 (d, 1H), 8.58 (d, 1H) 27 p. Such as c2h5 ch3 c2h5 162-163 1.26 (t, 3H), 1.50 (t, 3H), 2.30 (s, 3H), 3.00 (qt, 2H), 4.44 (q, 2H), 7.50 (m, 4H), 7.61 (td, 1H), 7.85 (dd, 2H), 7.96 (dd, 1H), 8.09 (dd? 1H), 8.45 (d, 1H), 8.62 (d, 1H) 28 CH3 Μ X ch3 y 05 N c2h5 ch3 ch3 150-152 1.48 (t, 3H), 2.14 (s, 6H), 2.29 (s, 3H), 2.38 (s, 3H), 2.51 (s, 3H), 4.42 (q, 2H), 6.95 (s, 2H), 7.44 (m, 2H), 7.94 (dd, 1H), 8.10 (m, 1H), 8.44 (d, 1H), 8.50 (m, 1H) 29 0 c2h5 ch3 ch3 110-113 1.45 (t? 3H ), 2.30 (s, 3H), 2.38 (s, 3H)? 2.50 (s, 3H), 4.40 (q, 2H), 7.25-7.50 (m, 6H), 7.90 (dd, 1H), 8.10 (dd, 1H), 8.40 (d, 1H), 8.50 (d, 1H) 30 p. Ch3 ch3 136-138 0.98 (t, 3H), 1.40 (t, 3H), 1.90 (tt, 2H), 2.30 (s, 3H), 2.50 (s, 3H), 4.30 (t, 2H), 7.50 ( m, 4H), 7.62 (td, 1H), 7.85 (dd, 2H), 7.98 (dd? 1H), 8.08 (dd, 1H) (Please read the precautions on the back before filling this page) • 、 may |

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 100 593357 A7B7 V. Description of invention (98)

(Please read the notes on the back before filling this page) R1 ~ C— (j) (j &gt; —C— ^ Table 2

Rj—C—Ar ^ Cr-Rj * Example Ail R1 R2 R2, state / melting point [° C] 'H-NMR, δ [ppm] 34 sjaaxx? Ch3 positive-C3H7 positive-C3H7 82-94 1.00 (t, 3H ), 1.62 (qt, 2H), 2.27 (s, 6H), 2.83 (t, 4H), 7.33 (d, 4H), 7.47 (d, 4H), 7.70 (d, 4H)? 7.72 (d, 4H) In Examples 35-36, the following sensitizers were used: S-1 4'-bis (diethylamino) -phenylacetophenone (EAB) S-2 2-isopropylthioxanthone and 4-isopropyl Mixture of thioxanthone (R ™ QUANTACURE ITX) This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 593357 A7 _B7_ V. Description of Invention (99) Example 35: (Please read the precautions on the back (Fill in this page again.) The photocurable composition used for the sensitivity test was prepared by mixing the following components: 200.0 parts by weight of an acrylated propylene-based copolymer (RTMACA200M, provided by Daicel Industries, Ltd., Solid content is 50% by weight) 15.0 parts by weight of dipentaerythritol hexaacrylate ((DPHA), provided by UCB Chemicals. 100.0 parts by weight of acetone in this mixture, 0.5% (based on solid content) sensitizer and 0.5% Or 2.0% ( Based on the solid content), the initiator to be tested is added and stirred. All operations are performed under yellow light. The composition is coated on a shao board. The solvent is heated in a convection oven at 80 ° C for 15 minutes. Remove. The thickness of the dried film is 25 // m. An acetate film is coated on this coating, and a standardized test negative film with 21 different optical densities (Stouffer step wedge) is placed thereon. Sample It is covered with a second ultraviolet transparent film and pressed on a metal plate by vacuum. The exposure is performed using a metal halide lamp (0RC, SMX 3000) at a distance of 60 cm for 40 seconds in the first test series and in the second series. 80 seconds, and 160 seconds in the third series. After exposure, the cover film and mask are removed, and the exposed film is at 30 ° C by a spray type developer (Walter Lemmen, T21 type) to A 1% sodium carbonate aqueous solution is developed for 180 seconds. The sensitivity of the initiator system used is determined by indicating the highest number of stages that are retained (ie, polymerized) after development. The higher the number of stages, the more sensitive the system being tested. The results are collected in Table 3. Zhang scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) 102 593357 A7B7 V. Description of the invention (100) Table 3 Photoinitiator example Photoinitiator concentration sensitizer Exposure to the following period of regeneration after 40 seconds 80 160 seconds 2 2.0%-13 15 17 3 2.0%-12 15 16 3 2.0% S-2 13 15 17 4 2.0%-12 14 16 5 0.5%-11 13 15 1 2.0%-14 17 19 8 2.0% S-2 12 15 16 9 0.5%-13 16 17 14 2.0%-14 17 18 10 2.0%-14 16 18 11 2.0%-12 14 16 12 0.5%-11 13 15 13 0.5%-15 18 20 18 2.0 %-8 1 13 16 2.0%-11 13 15 17 2.0%-8 10 12 19 2.0%-6 8 10 14 2.0%-13 15 17 21 2.0%-7 10 12 20 2.0%-5 8 9 24 2.0% -9 12 14 22 2.0%-10 13 14 25 2.0%-14 16 17 23 2.0%-11 13 14 15 2.0%-11 14 15 26 2.0%-13 16 17 27 2.0%-13 15 17 28 2.0%- 13 16 17 29 2.0%-13 16 17 30 2.0%-13 16 17 31 2.0%-10 13 14 (Please read the notes on the back before filling this page)

Ke I Example 36: Preparation of poly (benzyl methacrylate-co-fluorenyl acrylic acid) 24 g of benzyl methacrylate, 6 g of fluorenyl acrylic acid and 0.525 g of diazobisisobutyronitrile (AIBN) Dissolved in 90 ml of propylene glycol 1-monomethyl ether 2-acetate (PGMEA). The resulting reaction mixture was placed in a pre-heated oil bath at 80 ° C. After stirring at 80 ° C under nitrogen for 5 hours, the resulting viscous solution was cooled to room temperature and used without further purification. The solids content is about 25%. Sensitivity test The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 103 593357 A7 _ B7 _ V. Description of the invention (101) The photocurable composition used for the sensitivity test is made by mixing the following groups Made from: (Please read the precautions on the back before filling out this page) 200.0 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid (benzyl methacrylate: methacrylic acid = 80:20 Weight ratio), 25% propylene glycol 1-monofluorenyl ether 2-acetate (PGMEA) solution, 50.0 parts by weight of dipentaerythritol hexaacrylate (DPHA) was prepared as described above, provided by UCB Chemicals) 2.0 Parts by weight of the photoinitiator to be tested, 150.0 parts by weight of PGMEA, and optionally 1.2 parts by weight of the sensitizer. All operations were performed under yellow light. This composition was applied to an aluminum plate using an electric applicator having a wire-wound rod. The solvent was removed by heating in a convection oven at 100 ° C for 2 minutes. The thickness of the dry film is 2 // m. A standardized test negative film with 21 different optical densities (Stouffer step wedge) was placed with an air gap of about 100 // m between this film and the resist. The exposure was performed using a 250W over-pressure mercury lamp (USHI0, USH-250BY) with a distance of 15cm. The total exposure measured on the test negative film by an optical power meter (0RC UV Light Measure) UV-M02 with UV-35 detector is 1000mJ / cm2. After exposure, the exposed film was developed at 30 °: and developed by a spray type developer (Boundary &amp; 1 * 1 ^ 11111 ^ 11, Ding 21 type) with a 1% sodium carbonate aqueous solution for 100 seconds. The sensitivity of the initiator system used is determined by indicating the highest number of stages that are retained (i.e., polymerized) after development. The higher the number of stages, the more sensitive the system being tested. Result series This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 104 593357 A7 B7 5. The description of the invention (102) is shown in Table 4. Table 4 Example of photoinitiator No. of sensitizer Sl (EAB) S-2 (ITX) after regeneration at 1000mJ / cm2 without exposure 2 17--3 14 15 15 4 14--5 15--1 20- -7 15--9 14--14 18--10 18--12 16--18-13 13 16 13 14 14 17--12 14 18-19 21 16--20--12 24 18--22 15-16 25 20--23 15--15 18--26 20--27 19--28 19--29 20--30 19--31 17--(Please read the notes on the back before filling out this Page), ^ τ— This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) 105

Claims (1)

593357 A8 B8 C8 D8 VI. Application for Patent Scope No. 91112531 Patent Application Amendment for Patent Scope Revised December 15, 1992 1 · A compound of chemical formula I, π and ΠI as a photoinitiator Among them, the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperative printed Ri-based hydrogen, Cs-Cs cycloalkyl or alkyl, which are unsubstituted or substituted with one or more halogen, phenyl and / or CN; or Ri-based C2-C5 alkenyl; or Ri is phenyl, which is unsubstituted or substituted with one or more Cl_c6 alkyl, halogen, CN, OR3, SR4, and / or NR5R6; or R! Is C! -Cs Oxygen, benzyloxy; or phenoxy, which is unsubstituted or substituted with one or more (^-(: 6 alkyl and / or halogen; R2 and R2 'are each hydrogen independently; not A substituted alkyl group or an alkyl group substituted with one or more halogen, OR3, phenyl, and / or phenyl substituted with 0, 3, SR4, and / or NR5R6; or R2 and r2, are (: 3- (: 8 cycloalkyl; or C ^ -Cm alkyl, which is interrupted by one or more -0- and / or optionally by one or more halogens, 0r3, phenyl, and / or 0r3, Sr4 and / or NR] R6 substituted phenyl substitution; or r2 and r2 'are phenyl, which are unsubstituted or substituted with one or more alkyl, phenyl, halogen, Or3, SR4 and / or NR # 6substituted; or r2 and r2, which are c2-C2G alkylfluorenyl or benzamidine, which are not Or substituted with one or more C ^ -C ^ alkyl, phenyl, OR3, SR4, and / or NR5R6; R2 and R2, are C2-C12 alkoxy \ naphthyl 'which are optionally substituted with one or More -0-intermittent and / or select -106-.nnn I »n 1 n ϋ ϋ n I (Please read the precautions on the back of ts before filling out this page) Packing. This paper size applies to Chinese national standards (CNS ) A4 specification (210 X 297) 593357 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 The scope of patent application is substituted by one or more hydroxyl groups; or r2 and r2, are phenoxycarbonyl groups, It is unsubstituted or substituted with Ci-Cs alkyl, halogen, phenyl, or3, sr4 and / or NR5R6; or r2 and r2, CN, -CONR5R6, no2, CVC4 haloalkyl, s⑼m-Cl_c6 Alkyl; s (0) m-phenyl, which is optionally substituted with CrC12 alkyl or SOrCi-Q alkyl; or is so2o-phenyl 'which is optionally substituted with q-Cu alkyl; or two Phenylphosphinofluorenyl or 'mono- (Ci_C4alkyloxy) -scalyyl; or r2 and R2' are the following groups Aq is phenyl, naphthyl, benzamyl, or naphthyl, each of which is substituted 1 to 7 times with halogen, alkyl, C3-C8 cycloalkyl, benzyl, and / or phenoxycarbonyl; or Each is substituted with phenyl or phenyl substituted with one or more OR3, SR * and / or NRSR6; or each of them is substituted with C ^ -Cualkoxycarbonyl (which optionally Is one or more _〇- intermittently and / or optionally substituted with one or more hydroxyl groups); or each of them is substituted with OR3, SR4, SOR4, S02R4, and / or NR5R6, wherein the substituents 0R3, SRd NR5R6 optionally form a t or 6-membered ring via r3, r4, R5 and / or R6 with further substituents on the phenyl or naphthyl ring; or each of them is substituted with the following 107 This paper size applies to China National Standard (CNS) A4 (210 X 297) (please read the precautions on the back of ts before filling this page) 593357 A8 B8 C8 D8 But if R2 is not (A), (B) or (C) group, then An is phenyl, naphthyl, benzamyl or naphthyl, each of which is at least Mono- (CO) R7, (D), (E), or (F) group substitution; Ah is phenylene, naphthyl, phenylene dicarbonyl, or naphthyl dialkyl, each of which is halogen , Q-Cu alkyl, C ^ Cs cycloalkyl, benzyl, 0R3, sr4, so4, so2r4, and / or nr5r6 substituted 1 to 4 times; or each is-(CO) R7, ( D), (E) or (F) group substitution; but if R2 or R2, is not (A), (B) or (C) group and Ah is phenylene, naphthyl, diphenylyl or Arnaphthyldicarbonyl, then Ar2 is substituted with at least one of (C) r7, (D), (E) or (F) groups; if R2 is not hydrogen or (A), (B) or (C ), Each of which is replaced by at least one of-(c〇) R7, (E〇, (E) or (F) radical, (please read the precautions on the back of tt before filling this page) 丨 binding. Ar2 is additionally selected by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Or one is unsubstituted or substituted 1 to 4 times with halogen, alkyl, benzyl, 0r3, SR4, and / or NR # 6; or each is _ (c〇) R7, (D) , (E) or (F) group substitution; if the 112 series is (eight), (B) or (C) group, Ar2 is another 108. ) 593357 8888 ABCD patent application scope nJCCf. 'One of the parent is unsubstituted or substituted 1 to 4 times with halogen, C1-C12 alkyl, benzyl, OR3, SR4 and / or NR5R6, or each is-(CO) R7, ( D), (E) or (F) group substitution; or Ar2 series. CHg-M ^ CHi Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, each of which is unsubstituted or substituted 1 to 6 times with haloalkyl, benzyl, SR4 and / or NR5R6; among which the substituent 〇3 or NR # 6 is selected Form a 5- or 6-membered ring with one of the carbon atoms of the phenyl or pentenyl ring via I, Re Rs and / or &amp; or each of them is-(CO) R7, (D), ( E) or (F) group substitution; Ars is phenyl, naphthyl or coumarin group, each of which is _ prime, alkyl, c ^ -c: 8 cycloalkyl, benzyl and / or benzene Oxycarbonyl is substituted i to 7 times; or each is substituted with phenyl or phenyl substituted with one or more 0r3, and / or NRSR6; or each is applied at 109 paper sizes Chinese National Standard (CNS) A4 specification (210 X 297 issued) 593357 A8 B8 C8 D8 Patent application scope oxycarbonyl (selectively with one or more breaks and / or optionally with one or more hydroxyl groups Substitution) substitution; or each is substituted with or3, SR4, SOR4, S02R4, and / or NR5R6; and is a Ci-C ^ o alkylene, which is optionally substituted by one or more -0- discontinuities and And / or optionally with one or more More halogen, OR3, phenyl or phenyl substituted with OR3, SR4 and / or NR5R6; or Mi is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more alkyl groups , Phenyl, phenylene, OR3, SR4, and / or NR5R6; or Mi is as follows—MrCHrC (Η), (Please read the note on the back? Matters before filling out this page) · «丨-Installed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to print its optional sr4, sor4, S02R4 and / or NR5R6 are substituted 1 to 4 times; wherein the substituents 0r3, Sr4 or NR5R6 are optionally formed via R3, R4, R5 and / or R6 with one of the other phenyl ring carbon atoms. Or 6-membered ring; however, if Ar! Is phenyl, naphthyl, benzamyl, or naphthyl, each is not-(CO) -R7, (D), (E), or (F) Group substitution, then the (吣) or (H) group is optionally substituted 1 to 4 times with halogen, CVCu alkyl, benzyl, OR3, Sr4, SOR4, S02R4, and / or NR5R6; wherein the substituents are OR3, SR4, or NR5R6 optionally forms a 5- or 6-membered ring with one of the other phenyl ring carbon atoms via R3, R4, r5, and / or R6; M2 is a direct bond, Ci-Cn alkylene or Cyclohexyl; or 熥 2 series Cl-Cl0 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 issued). L. 110 593357 A8 B8 C8 D8 VI. Application scope of patent extended to the base or Ci- Cio Extender-X- Each of them is optionally substituted with one or more -0-breaks and / or optionally with one or more halogens, or3, phenyl, or a benzyl substituted with OR3, SR4, and / or NR5R6 ; Or M? Is phenylene or naphthyl or phenylene, each of which is unsubstituted or substituted with one or more CVC6 alkyl, phenyl, halogen, O3, Sr4, and / or NR5R6; Or M2 Cl-ClG alkylene_c (0) _x-, Ci_Ci () alkylene-XC (O)-, phenylene-C (0) -X-4 CVCio alkylene-phenylene- X-, M3 and M3 'are each a direct bond, C ^ -Cio alkylene or cyclohexyl; or M3 and M3' are CkCw alkylene or Ci-Cio alkylene-X-, each of which Is optionally substituted with one or more -0-breaks and / or optionally with one or more odontins, or3, phenyl or phenyl substituted with 0r3, sr4 and / or nr5r6; or m3 And m3 'is phenylene, naphthyl or phenylene-X_, each of which is unsubstituted or substituted with one or more Cl-c6 alkyl, phenyl, phenylene, or3, sr4, and / or nr5r6 substitution; or m3 and m3, are CVCn alkylene-c (0) -x-, Ci-Cw alkylene-XC (O)-, phenylene-c (o) -x-, cvc1 () Alkylene-benzene -X- or phenylene-C (0) -phenylene; printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, but if Ai * ι is Qinji, tea brewing or 2-R3O-phenyl 'each One is not substituted with (CO) R7, (D), (E) or (F) groups, J M3 and M3, non-CVC10 alkylene-X-, phenylene-X- or CrCK butane -Mendyl-X-; M4 and M4 'are each a direct bond, -0-, -S-, -NR5'- or -C0-; or M4 and M4' are -Y ^ CVCh) alkylene ) -Y'-, which selectively applies the Chinese National Standard (CNS) A4 specification (210 X 297 g) on a 111 paper scale-593357 A8 B8 C8 D8-0-intermittent and / Or optionally substituted with one or more halogen, or3, phenyl or phenyl substituted with OR3, SR4 and / or NR5R6; or M4 and M4 'are -Y-phenylene-Y'- or -Y -Naphthyl-Y'-, each of which is unsubstituted or substituted with one or more Ci-C6 alkyl, phenyl, halogen, 0r3, SR4 and / or NR5R6; or m4 and M4 ' -YJCVC # Dendroyl) -0-Dendphenyl-0- (CkC4Dendyl) -Y'- or -YJCVQ Dendyl) -0-Dendinyl_0- (Ci_C4Dendyl)- Y'_; or M4 and M4’-based -X-Ci-Ci〇 alkynyl-X-C (O)-'which is optionally selected from one or more -〇_ (Please read the note on the back ^: Fill in this page first) Install the consumer's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to print discontinuities; or M4 and M4 'are one-based groups, which are optionally based on iS elements, Ci-Cu alkyl groups , Phenylfluorenyl, or3, SR4, sor4, so2r4, and / or NR # 6 are substituted 1 to 4 times; wherein the substituents orr3, sr4, or NRsR6 are optionally via R3, R4, 1 ^ 5, and / or r6 Forms a 5- or 6-membered ring with one of the carbon atoms of another phenyl ring or a phenyl or naphthyl group attached to this group; M4 "is a direct bond, -0-, -s-, -NR5, -or -C0-; or M4 "is -Y ^ Ci-Cio), -Y'_, which is optionally interrupted with one or more and / or selectively with one or more halogen, 〇3, Phenyl or phenyl substituted with OR3, SR *, and / or NR ^ 6; or m4, which is · γ-phenylene-fluorene'- or -fluorene-naphthyl-fluorene, each of which Which is unsubstituted or substituted with one or more CKC6 alkyl, phenyl, halogen, OR3, Sr4, and / or nr5r6; or M4 "is -Xq-Cwalkylene-XC (O)-, which Select one or more -0-intermittent; 112 orders. This paper size applies Chinese National Standard (CNS) A4 regulations (210 X 297 mm) 593357 Α8 Β8 C8 D8 t, the scope of patent application X and X 'are -ο-, -s- or -NR5-, respectively; Y and Y' are direct bonds, -ο-, -s- or -NR5-; R3 is hydrogen, CVC20 alkyl or phenyl-CVC3 alkyl; or R3 is CVCs alkyl, which is -OH, -SH, -CN, C3-C6 alkenyloxy,- OCH2CH2CN, -OCi ^ CHKCCOCKCVC ^ alkyl), -〇 (CO)-(cvc4 alkyl), -0 (C0) -phenyl,-(CO) OH, and / or-(CCOCKCVQ alkyl) substitution; or R3 Is c2-c12 alkyl, which is interrupted by one or more of -ο-; or R3 is-(CH2CH20) n + 1H,-(CI ^ CI ^ COJCOHCi-Cs alkyl), CVC8 alkyl, c2 -c12 alkenyl, c3-c6 alkenyl, c3-c8 cycloalkenyl; or R3 benzyl, which is unsubstituted or substituted with one or more cvc6 alkyl, halogen, -OH, and / or cvc4 alkoxy substituted; or R3 is phenyl or naphthyl, each of which is unsubstituted or halogen, -0H, CVCu alkyl, CkCu alkoxy, phenoxy, CkCu alkylsulfanyl, benzene Sulfanyl, -NCCi-Cualkyl) 2 and / or diphenylamino; η is 1-20; R4 is hydrogen, CkCm alkyl, c2-c12 alkenyl, c3-c8 cycloalkyl, benzene -CVC3 alkyl; or R4 is CVCs alkyl, which is _OH, _SH, -CN, C3-C6 alkenyloxy, -OCH2CH2CN, -OCHKHdCCOCKCVQ alkyl), -0 ((: 0)-((^ -(: 4 alkyl), -O (CO) -phenyl,-(CO) OH, or-(CCOOCCVC ^ alkyl) substitution; or R4 is c2-c12 alkyl, which is substituted by one or more of- 0- or -S-discontinued; or R4 series (CH2CH20) n + 1H,-(CHzCP ^ OWCOHCVCs alkyl), CVQ alkyl group, c2-c12 alkenyl group, C3-C6 alkenyl group; or R4 series phenylfluorene Fluorenyl, which is unsubstituted or substituted with one or more CVC6 alkyl, halogen, -OH, CVC4 alkoxy-113-(Please read the precautions on the back before filling this page) Bureau employee consumer cooperative printed 593357 VI_ Printed by employee property cooperative of the Ministry of Economic Affairs Intellectual Property Bureau Α8 B8 C8 D8 Patent application scope or C ^ C4 alkylsulfanyl substitution; or r4 is phenyl or naphthyl, each of which is unsubstituted or substituted with halogen, Ci-Cu alkyl, Ci-Cu alkoxy , Phenyl-Ci-C: 3 alkoxy, phenoxy, c! -C12 alkylsulfanyl, phenylsulfanyl, -N (Ci-C12 alkyl), diphenylamino, -(00) 0 ((^-08alkyl),-(CCO-Ci-Cs: ^ 棊 or (CC ^ NCCi-Csalkyl) 2); R5 and R6 are each independently hydrogen, CVC20 alkyl, C2 -C4 hydroxyalkyl, c2-c1G alkoxyalkyl, c2-c5 alkenyl, C3-C8 cycloalkyl, phenyl-C3 alkyl, CVCs alkylfluorenyl, C3_C12-alkenyl, benzyl Fluorenyl; or r5 and r6 are phenyl or naphthyl, each of which is unsubstituted or substituted with Ci-Ci2 alkyl, methylamino or C1-C12 alkyl; or r5 and r6 together are CVC6 Alkylene, which is optionally substituted with -0- or -NR3- and / or optionally substituted with hydroxyl, Crq alkoxy, C2-C4 alkylfluorenyloxy or benzamyloxy; R5 is hydrogen, C1-C20 alkyl, C2-C4 alkyl, C2-C1G alkyloxy, C2-C5 alkenyl, C3-C8 cycloalkyl, phenyl-Ci-Cs alkyl, CVCs alkyl, Alkenyl Benzamidine; or r5, phenyl or naphthyl, each of which is unsubstituted or substituted with c! -C12 alkyl or CrCu alkoxy, or R5 'is 9-based; R7 is hydrogen, C1 -C20 alkyl; Ci-Cs alkyl, which is halogen, phenyl, -OH, -SH, -CN, c3-c6 η ^ -OCH2CH2CN &gt; -0CH2CH2 (C0) 0 (C1.C4 alkyl) , -CKCOXCi-C ^ alkyl), -0 (C0) -phenyl,-(C0) 0H or-(CCOCKCVC ^ alkyl) substitution; or C7-C12 alkyl, which is a 114-paper standard Applicable to China National Standard (CNS) A4 (210 · χ 297 mm) (Please read the precautions on the back before filling this page) 593357 A8 B8 C8 — D8, with one or more -0-interruptions applied for patents; or R7- (CH2CH2〇) n + 1H,-(CI ^ CI ^ OMCOHCkCs alkyl), c2-c12 alkenyl or c3-c8 ring gauge, or R7-based phenyl, biphenyl, or naphthyl, each of which is optionally one or more Ci-C6 alkyl, halogen, CN, OR3, SR4, SOR4, so2R4 Or nr5r6, wherein the substituents or3, sr4, or NR5R6 optionally form 5- or 6 via r3, r4, r5, and / or hexafluoro and one of the carbon atoms of the phenyl, biphenyl, or naphthyl ring -Membered ring; R8, R9, R8, and R9, each of which is hydrogen, CVCu alkyl, and its selectivity is one or more of halogen, phenyl, CN, -OH, -SH, CVC4 alkoxy,- (CO) OH or-(CCOCKCVC ^ alkyl) substitution; or R8, R9, R, and R9'-based phenyl, optionally substituted with one or more alkyl, halogen, CN, or3, sr4, or nr5r6 ; Or r8, r9, r8, and R9, which are halogen, CN, OR3, SR4, S0R4, S02R4, or NR5R6; wherein the substituents OR3, SR4, or NR5R6 are selectively connected to Ar via the R3, R4, R5, and / or R6 groups Carbon atom of phenyl, naphthyl, benzamyl or naphthyl One or a substituent R7 or one of the carbon atoms of naphthyl or phenyl of M3 forms a 5- or 6-membered ring; or R8 and R9 or R8, and r9. Please note on the back of the I Fill in item I | $ Pagination page it i L Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 10 ^ 11 ^ 12 ^ 13-c = c 一 c = c or ^ 14 ^ 15 0II C = C 一 C 一 〇— R10, Ru, R12, and Rl3 are each independently hydrogen, Ci-C12 alkyl, which are optionally selected from one or more halogen, phenyl, CN, -OH, -SH, CVC4 alkoxy,-( C0) 0H or-(CCOCHCVC ^ alkyl) substitution; or R10, 115 This paper size is applicable to China National Standard (CNS) A4 specifications (210 χ 297 issued) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 593357 A8 B8 C8 D8 VI. Patent application scope Rll, Rl2 and Rl3 are phenyl, which are optionally substituted with one or more CrC6 alkyl, halogen, CN, OR3, SR4 or NR5R6; or Rio, Ru, R12 and R13 are halogen , CN, OR3, SR4 or NR5R6; and R15 are each independently hydrogen or alkyl, which is optionally substituted with one or more halogen, phenyl, CN, —OH, —SH, CVQ Oxy,-(CO) OH or-((: 〇) 〇 ((: 1-0: 4 alkyl); or 1114 and 15 'phenyl, optionally with one or more Ci-C ^ Alkyl, halogen, cn, or3, sr4 or nr5r6; but (i) if Aq is phenyl, it is substituted with (E) and not additionally substituted with (D) or (F) and R2 is hydrogen , M4 is not directly built, S or NR5; (ii) If Aq is naphthyl, which is substituted with (e) and is not additionally substituted with (d) or (F), then M4 is not directly built, S, 0 or nr5; (iii) if M4 is 0 and R2 is hydrogen, then Ar! Is not substituted with (E) group and is not additionally substituted with (D) or (F) group and at the same time, it is substituted with 0r3 or with SR4, NR5R6, phenyl, _ (c〇) R7 or S02R7 substituted phenyl; (iv) if An is phenyl, it is substituted with-(c〇) r7 without additional (D) or (F) R2 is not hydrogen; (v) if Aq is phenyl, which is substituted with-(C〇) r7 and is not additionally substituted with (D) or (F) and &amp; non-hydrogen, then non-benzene (Vi) if Ar! Is naphthyl, which is substituted with — (C〇) R7 and is not additionally substituted with (D) or (F), then Han 7 is not phenyl or Ci_Cii Alkyl The polymeric composition comprising: -116-- This paper scale applicable Chinese National Standard (CNS) A4 size (210 X 297 male hair) (Please Note Mti then fill out the back of this page) / 、 Applicable patent scope (a) at least one ethylenically unsaturated photopolymerizable compound, and (b) at least one of the compounds of chemical formulae Π, Π, and ΙΠ as photoinitiator as in item 1 of the patent application scope, where In addition to the photoinitiator (b), the composition includes at least one further photoinitiator (C) and / or other additives (d), and 'the composition system includes the composition as a basis, 〇〇〇 5 to 25% by weight of the photoinitiator, or the photoinitiator (... and. 3. A method for photopolymerizing a compound containing an ethylenically unsaturated double bond, which includes a composition such as the second item in the scope of patent application The object is irradiated with electromagnetic radiation in the range of 150 to 600 nm or with an electron beam or with x-rays. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Tinted and untinted paints and lacquers, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coatings, photoresists for electronic products, such as plating resists, etching resists Agent, liquid and dry film, solder resist Resistors used to prepare color filters for various display applications or structures used in the production methods of plasma display panels, electroluminescence displays, and LCDs are used as components for packaging electrical and electronic components. To manufacture magnetic recording materials, micromechanical parts, wave guides, optical switches, plating masks, etching masks, color verification systems, fiberglass cable coatings, and screen printing printing stencils for use in stereolithography Printing technology to prepare three-dimensional objects, and as image recording materials, especially for all-photographic recording, microelectronic circuits, decoloring materials, poem image recording materials = decoloring materials, used for microencapsulated image recording materials, Photoresist material for direct imaging of ultraviolet and visible light lasers, used to form ------------117-This paper size is applicable to China National Standard (CNS) A4 specifications ⑵Q ϋ--the intellectual property of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Bureau ΙΓ ~ Τ ~~-~~ ----- / 、、 Patent application scope of the printed circuit board in order to build up the photoresist material of the dielectric layer in the layer. 5 · If applied The composition of the second item of the invention is coated on at least the surface of the coated substrate to form the coated substrate. 6. As the photoinitiator of the application of the patent _ item 1 The compounds of the formulae Π and ΠI are included in a photosensitive resin containing a polyfunctional acetic acid monomer and an organic polymer adhesive. Among them, the filter is provided by a transparent substrate with red, The green and blue pixels and the black matrix all include the photosensitive resin and colorant, and are prepared by providing a transparent electrode on the surface of the substrate or the surface of the color filter layer. 118 This paper size is applicable to Chinese national standards ( CNS) A4 (21〇χ 297 mm)